Palladium-Catalyzed Aerobic Oxidative Coupling of ortho-(Alkynyl

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Palladium-Catalyzed Aerobic Oxidative Coupling of ortho(Alkynyl)styrenes with Allylic Alcohols via 6-endo-dig Cyclization: Regioselective Construction of Polysubstituted Naphthalenes Perla Ramesh, and Gedu Satyanarayana J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b01240 • Publication Date (Web): 15 Aug 2019 Downloaded from pubs.acs.org on August 15, 2019

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The Journal of Organic Chemistry

Palladium-Catalyzed Aerobic Oxidative Coupling of ortho-(Alkynyl)styrenes with Allylic Alcohols via 6-endo-dig Cyclization: Regioselective Construction of Polysubstituted Naphthalenes

Perla Ramesh, Gedu Satyanarayana*

Department of Chemistry, Indian Institute of Technology Hyderabad, Kandi–502285, Sangareddy, Telangana, India.

ABSTRACT An efficient protocol is described for the regioselective construction of polysubstituted functionalized naphthalenes from easily accessible ortho-(alkynyl)styrenes under mild reaction conditions. The reaction proceeds via cycloaromatization and intermolecular coupling of ortho(alkynyl)styrenes with allylic alcohols catalyzed by PdCl2. Notably, the reaction is successful under open air as the green oxidant source. A range of functional groups (F, Cl, Br, NO2, and ester) including protecting free OH groups was found to be compatible.

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INTRODUCTION Alkyne-directed transition-metal catalyzed transformations have gained importance, particularly, to accomplish a diverse array of cyclic products.1 To this relevance, alkyne moiety tends to chelate the metal canter of the active catalyst, thus, facilitate the construction of multiple CC and Cheteroatom bonds.2 During the course of CC triple bond activation by metal catalyst, nucleophilic attack (i.e. by acetates,3 amines,4 halides,5 and electron-rich carbon nucleophiles6) would take place across triple bond and generates the vinyl metal species, which in turn can combine with olefins under oxidative Heck coupling in a single-pot operation. In this context, several interesting methods have been developed for the construction of cyclic products by using electron deficient olefins as coupling partners for the establishment of intermolecular CC bond.7 Recently, there were several interesting reports witnessed that allylic alcohols could also be served as useful coupling partners under intermolecular oxidative Heck coupling.8 Indeed, allylic alcohols are useful starting materials due to their abundance, inexpensive and easy preparation. Moreover, they are unique and can be employed as alkene as well as ketone equivalents depending upon the reaction conditions.9 However, palladium catalyzed oxidative couplings of alkynes, specifically, with allylic alcohols were scarcely explored 10 and thus, there is sufficient scope for the developing new and efficient domino synthetic strategies. Polysubstituted naphthalenes have attracted much attention owing to their biological and pharmaceutical importance. Natural products that consist naphthalene unit possesses anticancer, antimicrobial, antibacterial and anti-inflammatory activities (Figure 1).11 Additionally, these structural motifs can be found in numerous electronic and optical materials because of their unique photochemical, photoconductivity and electroluminescent properties.12 Moreover, these scaffolds constitute the main core of many chiral ligands.13


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Figure 1. Representative bioactive molecules of naphthalenes.

Accordingly, significant efforts have been devoted to the blooming of elegant methods for the regioselective construction of polysubstituted naphthalene structures in the past decades. The contribution of catalysis under mild reaction conditions and high compatibility with different functional groups to this field being particularly remarkable and highly desirable.14 Among these strategies, an efficient and powerful synthetic methodology is based on the benzo-fused 1,3-dien5-ynes catalytic cycloaromatization process.15,16 Moreover, 1,3-dien-5-ynes have recently emerged as useful starting materials for the preparation of diverse hetero- and carbo-cycles, and they have been extensively used as attractive precursors to the establishment of the aromatic rings via cycloaromatization.17 Meanwhile, various metal complexes (Pd, Au, Pt, Ru, Rh, Ag, W, In, Zn and Fe/Cu)16 have been employed for the synthesis of naphthalenes from benzo-fused 1,3dien-5-ynes. In 2010, Loh’s group developed Pd-catalyzed intramolecular annulation of ortho(alkynyl)styrenes and intermolecular oxidative with electron deficient olefins, providing convenient access to substituted naphthalene derivatives.16g As part of our ongoing research



towards palladium-catalyzed domino reactions including cross-coupling reactions,18 herein we report a novel PdCl2-catalyzed intermolecular oxidative coupling of ortho-(alkynyl)styrenes with allylic alcohols for the efficient synthesis of polysubstituted naphthalenes. This approach allowed regioselective intramolecular cycloaromatization between alkene and alkyne moieties of ortho(alkynyl)styrenes and subsequent coupling with allylic alcohols.

RESULTS AND DISCUSSION At the outset of our investigation, we commenced optimization studies with easily available 1-(phenylethynyl)-2-(1-phenylvinyl)benzene 1a (0.1 mmol) and 1-(4-ethylphenyl)prop2-en-1-ol 2a (0.3 mmol) as the substrates and PdCl2 (0.02 mmol) as a catalyst in dimethyl sulfoxide (1 mL) solvent under open-air atmosphere for 12 h at 80 °C. We were pleased to observe that 41% yield of the desired product 3-(2,4-diphenylnaphthalen-1-yl)-1-(4ethylphenyl)propan-1-one 3aa was obtained (Table 1, entry 1). Inspired by this delighting result, we extensively investigated to ascertain the efficiency of various palladium catalysts (Table 1, entries 2−6). Screening of different Pd(II)-catalysts including PdCl2(CH3CN)2, PdCl2(PPh3)2 and Pd(OAc)2, revealed that none of them were more efficient than PdCl2 (Table 1, entries 2−4). However, the desired product 3aa was not detected when Pd(0)-catalysts such as Pd(PPh3)4 and Pd2(dba)3 were employed, and unreacted starting materials were recovered (Table 1, entries 5 & 6). Further evaluation of solvents such as DMF, DMA, DCE, MeCN, toluene, and H2O indicated 1,4-dioxane to be the most suitable one for this transformation, affording the product 3aa in 72% yield (Table 1, entries 7−13). Moreover, the loading of catalyst and allylic alcohol was also tested. A yield of 71% could be obtained in the presence of 10 mol % of PdCl2 with 3 equiv of allylic alcohol 2a in dioxane by prolonging the reaction time to 24 h at 80 oC (Table 1, entries


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14−16). Examination of the reaction temperature showed that lower yields were obtained at 120 and 25 oC (Table 1, entries 17 & 18). To our delight, the yield of the product 3aa was increased to 79% when the temperature was decreased to 60 °C (Table 1, entry 19). It is important to note that molecular oxygen did not improve the yield of 3aa and gave the result comparable to those obtained under open-air conditions (Table 1, entry 20). When the reaction was performed under N2 atmosphere, only 14% yield of the product was obtained (entry 21). Finally, the desired product 3aa could not be achieved in the absence of PdCl2 catalyst, obviously verifying the necessity of a palladium catalyst (Table 1, entry 22).

Table 1. Screening of the Reaction Conditions.a

temp (oC)

time (h)

3aa (%)b

DMSO DMSO DMSO DMSO DMSO DMSO DMF

80 80 80 80

12 12 12 12

41 26 Trace

80 80 80

12 12 12

DMA Dioxane DCE CH3CN Toluene H 2O Dioxane Dioxane Dioxane Dioxane

80

12

80 80 80 80

12 12 12 12

80 80 80 80 120

12 34 24 24 24

entry

catalyst

solvent

1 2 3 4 5 6 7

PdCl2 PdCl2(CH3CN)2 PdCl2(PPh3)2 Pd(OAc)2 Pd(PPh3)4 Pd2(dba)3 PdCl2

8 9 10 11 12 13 14 15 16 17

PdCl2 PdCl2 PdCl2 PdCl2 PdCl2 PdCl2 PdCl2 PdCl2 PdCl2 PdCl2


c NR NR c c 72 NR 57 c 22 63d 71e 46e,f 62e


18 19 20 21 22

PdCl2 PdCl2 PdCl2 PdCl2 No catalyst

Dioxane Dioxane Dioxane Dioxane Dioxane

25 60 60 60 60

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24 24 24 24 24

30e 79e 74e,g 14h NR

a

Reaction conditions: Compound 1a (0.1 mmol), compound 2a (0.3 mmol), PdCl2 (20 mol%) under open air

atmosphere at 80 oC, 12 h. bIsolated yields. cStarting material was decomposed. dPdCl2 (5 mol%) was used. ePdCl2 (10 mol%) was used. fCompound 2a (0.2 mmol) was used. gUnder molecular oxygen. hReaction was conducted under N2 atmosphere.

With the optimal conditions in hand (Table 1, entry 19), we next systematically explored the scope of this Pd-catalyzed intermolecular oxidative coupling reaction, using a variety of ortho(alkynyl)styrene substrates 1a-v with 1-(4-ethylphenyl)prop-2-en-1-ol 2a as the coupling partner to accomplish functionalized naphthalenes. As highlighted in Table 2, a large array of internal enynes are compatible with this reaction, including those with electron donating 1b–1d as well as withdrawing (1e–1h) substituents. Various phenyl alkynes with different functional groups such as methyl, methoxy, fluoro and chloro on the phenyl ring of the internal alkyne reacted smoothly with 2a to render the corresponding unsymmetrical naphthalene ketones 3ba–3fa in good yields (69-86%), thus offering a wide range of opportunities for further functionalization. Significantly, the reaction was also feasible with strong electron withdrawing group substituents, such as nitro and ester groups (Table 2, 3ga & 3ha). Thiophene-tethered heterocyclic alkyne substrate 1i also reacted well, thereby producing heteroaryl-substituted naphthalene derivative 3ia efficiently in 66% yield. It is worth highlighting that relatively less reactive aliphatic alkynes also could be tolerated well and the desired products 3ja–3la. Delightedly, substrate 1m containing free hydroxyl group was also well tolerated and gave naphthalene 3ma in 68% yield, eliminating the need for protecting groups. A good yield 70% was achieved for compound 3na,


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wherein phenyl moiety (R2) was exchanged by electron donating methoxyphenyl group 1m under established reaction conditions. Similarly, the phenyl group (R2) was replaced with an aliphatic (ethyl) group, confirming the reaction efficiency and 3oa was afforded in 61% yield. Moreover, substrate 1p, in which both the aryl groups (R2 and R4) were replaced with aliphatic groups, could also afford the corresponding naphthalene 3pa, albeit with a relatively lower yield (35%). Next, we studied a few substrates containing different substituents (R1) on the phenyl ring of enyne to show the versatility of this reaction. Gratifyingly, this strategy was also equally applicable to the substrates bearing alkoxy substituents on the benzene ring of enyne such as 1q and 1r affording the desired naphthalenes 3qa, and 3ra in good yields as 81 and 74%, respectively. Additionally, a fluoro-functionalized substrate 1s was also examined, and corresponding coupling product 3sa was isolated in 67% yield, increasing the scope for a further derivation of the C−halogen bond. It is noteworthy that the reaction of substrate 1t bearing methyl group at R3 position also proceeded well and was converted into naphthalene 3ta in 64% yield. However, no desired products were obtained with simple styrene [1-(phenylethynyl)-2vinylbenzene (R2 and R3 = H)] or terminal alkyne [1-ethynyl-2-(1-phenylvinyl)benzene (R3 and R4 = H)] was employed as substrates in the reaction.



Table 2. The scope of ortho-(alkynyl)styrenes.a,b

a

Reaction conditions: Compound 1 (0.2 mmol), compound 2a (0.6 mmol), PdCl2 (10 mol%) under open air

atmosphere at 60 oC, 12 h. bIsolated yields. cThe reaction performed in 5 mmol scale.


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Next, we used ortho-(alkynyl)styrenes to examine the intermolecular Pd-catalyzed crosscoupling reaction with a series of allylic alcohols (Table 3). To our delight, phenyl substituted allylic alcohol reacted with 1a and 1u in dioxane, yielding naphthalenes 3ab and 3ub in 75% and 63% yields, respectively. Moreover, an extended aromatic entity such as naphthyl allylic alcohol 2c also smoothly underwent this reaction and provided product 3ac in 72% yield. Aromatic ring possessing electron-rich substituents such as alkoxy groups were smoothly reacted under standard reaction conditions and gave the desired products 3jd, 3ae, and 3jf in moderate yields. Notably, aromatic ring possessing halogen substituents were also good coupling partners. Substituents such as bromo and chloro on the aromatic ring were compatible with the reaction, furnished the products 3ag and 3nh in 47% and 41% yields, respectively. Along these lines, it is notable that halide substituted naphthalene ketone derivatives would be potentially useful for further synthetic transformations by traditional metal catalyzed cross-coupling strategies. Heterocyclic allylic alcohol substrates 2i and 2j were proven to be appropriate candidates, delivering the corresponding products 2ai (62%) and 2aj (64%). Gratifyingly, the standard reaction conditions proved to tolerate n-pentyl 2k and cyclohexyl 2l aliphatic allylic alcohols, as well, as demonstrated by the isolation of 3nk and 3fl in 66% and 60% yields, respectively. To our delight, 4-(1-hydroxyallyl)phenol substrate 2m with a free hydroxyl group also could be used as the coupling partner to provide the desired product 3am in 69% yield. It is worth noting that the reactions were unsuccessful with substituted allylic alcohol coupling partners [i.e. the reactions with (i) 3-methyl-1-phenylbut-2-en-1-ol and (ii) (E)-4-phenylbut-3-en-2-ol as olefin coupling partners].



Table 3. The scope of allylic alcohols.a,b

a

Reaction conditions: Compound 1 (0.2 mmol), compound 2 (0.6 mmol), PdCl2 (10 mol%) under

open air atmosphere at 60 oC, 12 h. bIsolated yields.

A tentative plausible catalytic cycle is proposed for the Pd-catalyzed intermolecular oxidative coupling of inactivated ortho-(alkynyl)styrenes with alkenyl alcohols based on the above results and previous literature (Scheme 1).8-10 The coordination of Pd(II) species to the internal C-C triple bond of substrate 1 provides intermediate A, which subsequently undergoes intramolecular 6-endo-dig cyclization to afford a key naphthylpalladium intermediate C, because the formed carbocation B can be stabilized by a benzene ring. Oxidative insertion of the allylic alcohol


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coupling partner 2 into the carbon-palladium bond of C generates the intermediate D, which undergoes β-hydride elimination to form intermediate E. Finally, the intermediate E produces the desired naphthalene 3, and the Pd(II) is regenerated by molecular oxygen oxidizing agent, to complete the catalytic cycle.

Scheme 1. Plausible reaction mechanism.

CONCLUSIONS In conclusion, we have developed a novel Pd-catalyzed 6-endo-dig cycloaromatization of ortho(alkynyl)styrenes and oxidative coupling with allylic alcohols under the open-air atmosphere, delivering a wide range of polysubstituted naphthalene ketones. The process enabled the construction of two new C–C bonds with broad substrate scope. The devised methodology is



highly compatible with various functional groups, including F, Cl, Br, free hydroxyl, NO2 and ester under these mild conditions.

EXPERIMENTAL SECTION General methods: IR spectra were recorded on a Bruker Tensor 37 (FTIR) spectrophotometer. 1H NMR spectra were recorded on Bruker Avance 400 (400 MHz) spectrometer at 295 K in CDCl3; chemical shifts (δ ppm) and coupling constants (Hz) are reported in standard fashion with reference to internal standard tetramethylsilane (TMS) (δH = 0.00 ppm). 13C{1H} NMR spectra were recorded on Bruker Avance 400 (100 MHz) spectrometer at RT in CDCl3; chemical shifts (δ ppm) are reported relative to CHCl3 [δC = 77.00 ppm (central line of the triplet)]. In the 1H-NMR, the following abbreviations were used throughout: s = singlet, d = doublet, t = triplet, q = quartet, qui = quintet, sept = septet, dd = doublet of doublets, m = multiplet and br. s = broad singlet. The assignment of signals was confirmed by 1H,

13

C{1H}, and DEPT spectra. High-resolution mass

spectra (HR-MS) were recorded on an Agilent 6538 UHD Q-TOF electron spray ionization (ESI) mode and atmospheric pressure chemical ionization (APCI) modes. All small-scale reactions were carried out by using a Schlenk tube. Reactions were monitored by TLC on silica gel using a combination of hexane and ethyl acetate as eluents. Solvents were distilled prior to use; petroleum ether with a boiling range of 60 to 80 C was used. Pyridinium chlorochromate (PCC), Pd(OAc)2, potassium tert-butoxide and, triphenylphosphine (TPP), K2CO3 and PdCl2 were purchased from Sigma-Aldrich and used as received. ortho-Bromo benzaldehydes, aryl halides, alkyl halides and 1-alkynes were purchased from Sigma-Aldrich/TCI/local sources and used as


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received. Acme’s silica gel (60–120 mesh) was used for column chromatography (approximately 20 g per one gram of crude material).

General Procedure for the Synthesis of ortho-(Alkynyl)styrenes (1): The appropriate alkyne (1.1 mmol) was added to a solution of the corresponding ortho-bromo styrene19 (1 mmol), K2CO3 (1.5 mmol), CuI (0.05 mmol), Pd(OAc)2 (0.03 mmol), triphenylphosphine (0.06 mmol) in DMF (5 mL). The resulting mixture was heated in a 100 °C oil bath with rapid stirring until the ortho-bromo styrene was consumed as determined by TLC. The crude mixture was partitioned between water and CH2Cl2 and the solvents were removed under reduced pressure. The residue was purified by flash chromatography using mixtures of hexane and EtOAc as eluents to obtain the corresponding ortho-(alkynyl)styrenes (1) which were used in the next step. The data of known compounds 1a,16c 1d16c 1u7b are consistent with the previously reports and the copies of their 1H NMR spectra were included in the Supporting Information. Characterization data of new compounds were also provided herein.

1-(Phenylethynyl)-2-(1-phenylvinyl)benzene (1a):16c Yield: 86% (241 mg). Rf = 0.7 (petroleum ether/ethyl acetate 90:10). Physical aspect: yellow oil.

1-(1-Phenylvinyl)-2-(m-tolylethynyl)benzene (1b): Yield: 85% (250 mg). Rf = 0.7 (petroleum ether/ethyl acetate 90:10). Physical aspect: yellow oil. 1

H NMR (400 MHz, CDCl3): δ = 7.58–7.51 (m, 1H, Ar–H), 7.38–7.23 (m, 8H, Ar–H), 7.10 (t, J

= 7.6 Hz, 1H, Ar–H), 7.03 (d, J = 7.6 Hz, 1H, Ar–H), 6.94 (d, J = 7.5 Hz, 1H, Ar–H), 6.89 (s,



1H, Ar–H), 5.78 (d, J = 1.2 Hz, 1H, =CH), 5.41 (d, J = 1.1 Hz, 1H, =CH), 2.26 (s, 3H, CH3) ppm. 13C{1H} NMR (100 MHz, CDCl3): δ = 149.0 (Ar–C), 144.2 (Ar–C), 140.9 (Ar–C), 137.6 (Ar–C), 132.5 (Ar–CH), 132.1 (Ar–CH), 130.1 (Ar–CH), 128.8 (Ar–CH), 128.4 (Ar–CH), 128.2 (2 × Ar–CH), 128.1 (Ar–CH), 127.9 (Ar–CH), 127.5 (Ar–CH), 127.4 (Ar–CH), 127.1 (2 × Ar– CH), 123.0 (Ar–C) , 122.6 (Ar–C), 116.2 (=CH2), 93.8 (C), 88.4 (C), 21.1 (CH3) ppm. HRMS (ESI) calculated [M+H]+ for C23H19: 295.1481, found: 295.1482.

1-(1-Phenylvinyl)-2-(p-tolylethynyl)benzene (1c): Yield: 87% (257 mg). Rf = 0.7 (petroleum ether/ethyl acetate 90:10). Physical aspect: yellow oil. 1

H NMR (400 MHz, CDCl3): δ = 7.61–7.51 (m, 1H, Ar–H), 7.37–7.23 (m, 8H, Ar–H), 7.01 (d, J

= 1.3 Hz, 4H, Ar–H), 5.77 (d, J = 1.0 Hz, 1H, =CH), 5.40 (d, J = 1.0 Hz, 1H, =CH), 2.28 (s, 3H, CH3) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 149.0 (Ar–C), 144.1 (Ar–C), 140.9 (Ar–C),

138.0 (Ar–C), 132.5 (Ar–CH), 131.3 (2 × Ar–CH), 130.1 (Ar–CH), 128.8 (2 × Ar–CH), 128.2 (2 × Ar–CH), 128.0 (Ar–CH), 127.5 (Ar–CH), 127.4 (Ar–CH), 127.1 (2 × Ar–CH), 122.7 (Ar–CH), 120.2 (Ar–CH), 116.1 (=CH2), 93.77 (C), 88.1 (C), 21.4 (CH3) ppm. HRMS (ESI) calculated [M+H]+ for C23H19: 295.1481, found: 295.1483.

1-((4-Methoxyphenyl)ethynyl)-2-(1-phenylvinyl)benzene (1d) 16c Yield: 89% (276 mg). Rf = 0.7 (petroleum ether/ethyl acetate 90:10). Physical aspect: yellow oil.

1-((3-Fluorophenyl)ethynyl)-2-(1-phenylvinyl)benzene (1e):


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Yield: 74% (220 mg). Rf = 0.7 (petroleum ether/ethyl acetate 90:10). Physical aspect: yellow oil. 1

H NMR (400 MHz, CDCl3): δ = 7.58–7.52 (m, 1H, Ar–H), 7.39–7.24 (m, 8H, Ar–H), 7.18–7.12

(m, 1H, Ar–H), 6.95–6.87 (m, 2H), 6.78–6.73 (m, 1H), 5.78 (d, J = 1.1 Hz, 1H, =CH), 5.39 (d, J = 1.1 Hz, 1H, =CH) ppm. 13C{1H} NMR (100 MHz, CDCl3): δ = 162.2 (d, JC-F = 244.5 Hz, Ar– C), 148.9 (Ar–C), 144.4 (Ar–C), 140.8 (Ar–C), 132.6 (Ar–CH), 130.2 (Ar–CH), 129.5 (d, JC-F = 8.7 Hz, Ar–CH), 128.6 (Ar–CH), 128.2 (2 × Ar–CH), 127.6 (Ar–CH), 127.5 (Ar–CH), 127.2 (d, JC-F = 2.9 Hz, Ar–CH), 127.1 (2 × Ar–CH), 125.1 (d, JC-F = 9.5 Hz, Ar–C), 122.0 (Ar–CH), 118.2 (d, JC-F = 21.2 Hz, Ar–CH), 116.3 (=CH2), 115.2 (d, JC-F = 21.2 Hz, Ar–CH), 92.3 (C), 89.6 (C) ppm. HRMS (ESI) calculated [M+H]+ for C22H16F: 299.1231, found: 299.1239.

1-Chloro-2-((2-(1-phenylvinyl)phenyl)ethynyl)benzene (1f): Yield: 75% (250 mg). Rf = 0.6 (petroleum ether/ethyl acetate 90:10). Physical aspect: yellow oil. 1

H NMR (400 MHz, CDCl3): δ = 7.63 (dd, J = 7.3, 1.5 Hz, 1H, Ar–CH), 7.39–7.23 (m, 9H, Ar–

CH), 7.19–7.03 (m, 3H, Ar–CH), 5.82 (s, 1H, =CH), 5.45 (s, 1H, =CH) ppm. 13C{1H} NMR (100 MHz, CDCl3): δ = 148.4 (Ar–C), 144.2 (Ar–C), 140.8 (Ar–C), 135.6 (Ar–C), 133.3 (Ar–CH), 133.0 (Ar–CH), 130.0 (Ar–CH), 129.03 (Ar–CH), 128.96 (Ar–CH), 128.6 (Ar–CH), 128.2 (2 × Ar–CH), 127.5 (Ar–CH), 127.4 (Ar–CH), 127.1 (2 × Ar–CH), 126.1 (Ar–CH), 123.2 (Ar–C), 122.2 (Ar–C), 116.5 (=CH2), 93.8 (C), 90.0 (C) ppm. HRMS (ESI) calculated [M+H]+ for C22H16Cl: 315.0935, found: 315.0929.

1-((4-Nitrophenyl)ethynyl)-2-(1-phenylvinyl)benzene (1g): Yield: 69% (224 mg). Rf = 0.5 (petroleum ether/ethyl acetate 90:10). Physical aspect: yellow solid. 1H NMR (400 MHz, CDCl3): δ = 8.13–8.02 (m, 2H, Ar–CH), 7.59–7.54 (m, 1H, Ar–CH),



7.45–7.26 (m, 8H, Ar–CH), 7.21–7.15 (m, 2H, Ar–CH), 5.81 (d, J = 1.0 Hz, 1H, =CH), 5.40 (d, J = 1.0 Hz, 1H, =CH) ppm.

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C{1H} NMR (100 MHz, CDCl3): δ = 148.8 (Ar–C), 146.7 (Ar–C),

144.7 (Ar–C), 140.6 (Ar–C), 132.8 (Ar–CH), 132.0 (2 × Ar–CH), 130.3 (Ar–CH), 130.2 (Ar–C), 129.3 (Ar–CH), 128.3 (2 × Ar–CH), 127.7 (Ar–CH), 127.6 (Ar–CH), 127.0 (2 × Ar–CH), 123.3 (2 × Ar–CH), 121.3 (Ar–C), 116.5 (=CH2), 94.1 (C), 91.7 (C) ppm. HRMS (ESI) calculated [M]+ for C22H15NO2: 325.1097, found: 325.1108.

Methyl 4-((2-(1-phenylvinyl)phenyl)ethynyl)benzoate (1h): Yield: 70% (237 mg). Rf = 0.5 (petroleum ether/ethyl acetate 90:10). Physical aspect: colourless oil. 1H NMR (400 MHz, CDCl3): δ = 7.93–7.86 (m, 2H), 7.57 (dt, J = 7.3, 1.2 Hz, 1H), 7.40– 7.25 (m, 8H), 7.17–7.12 (m, 2H), 5.80 (d, J = 1.1 Hz, 1H), 5.41 (d, J = 1.1 Hz, 1H), 3.90 (s, 3H) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 166.6 (C=O), 148.9 (Ar–C), 144.5 (Ar–C), 140.8

(Ar–C), 132.7 (Ar–CH), 131.3 (2 × Ar–CH), 130.2 (Ar–CH), 129.2 (Ar–C), 129.1 (2 × Ar–CH), 128.8 (Ar–CH), 128.2 (2 × Ar–CH), 128.0 (Ar–C), 127.6 (Ar–CH), 127.5 (Ar–CH), 127.1 (2 × Ar–CH), 121.9 (Ar–C), 116.4 (=CH2), 92.8 (C), 91.7 (C), 52.15 (OCH3). HRMS (ESI) calculated [M+H]+ for C24H19O2: 339.1380, found: 339.1379.

3-((2-(1-Phenylvinyl)phenyl)ethynyl)thiophene (1i): Yield: 75% (215 mg). Rf = 0.7 (petroleum ether/ethyl acetate 90:10). Physical aspect: yellow oil. 1

H NMR (400 MHz, CDCl3): δ = 7.55–7.49 (m, 1H, Ar–H), 7.37–7.23 (m, 8H, Ar–H), 7.13 (dd,

J = 4.9, 3.0 Hz, 1H, Ar–H), 7.10–7.06 (m, 1H, Ar–H), 6.79 (d, J = 4.9 Hz, 1H, Ar–H), 5.75 (s, 1H, =CH), 5.39 (s, 1H, =CH) ppm. 13C{1H} NMR (100 MHz, CDCl3): δ = 149.0 (Ar–C), 144.2 (Ar–C), 140.9 (Ar–C), 132.4 (Ar–CH), 130.1 (Ar–CH), 129.7 (Ar–CH), 128.4 (Ar–CH), 128.2


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(2 × Ar–CH, Ar–CH), 127.5 (Ar–CH), 127.4 (Ar–CH), 127.1 (2 × Ar–CH), 124.9 (Ar–CH), 122.4 (Ar–C), 122.2 (Ar–C), 116.2 (=CH2), 88.8 (C), 88.2 (C) ppm. HRMS (ESI) calculated [M+H]+ for C20H15S: 287.0889, found: 287.0904.

1-(Hex-1-yn-1-yl)-2-(1-phenylvinyl)benzene (1j): Yield: 71% (185 mg). Rf = 0.8 (petroleum ether/ethyl acetate 90:10). Physical aspect: yellow oil. 1

H NMR (400 MHz, CDCl3): δ = 7.45–7.37 (m, 1H, Ar–H), 7.33–7.19 (m, 8H, Ar–H), 5.72 (s,

1H, =CH), 5.34 (s, 1H, =CH), 2.11 (t, J = 6.5 Hz, 2H, CH2), 1.31–1.17 (m, 4H, 2 × CH2), 0.81 (t, J = 6.8 Hz, 3H, CH3) ppm. 13C{1H} NMR (100 MHz, CDCl3): δ = 149.2 (Ar–C), 144.1 (Ar–C), 141.0 (Ar–C), 132.5 (Ar–CH), 129.9 (Ar–CH), 128.0 (2 × Ar–CH), 127.4 (Ar–CH), 127.3 (Ar– CH), 127.2 (Ar–CH), 126.9 (2 × Ar–CH), 123.3 (Ar–C), 115.7 (=CH2), 94.8 (C), 79.6 (C), 30.5 (CH2), 21.8 (CH2), 19.0 (CH2), 13.6 (CH3) ppm. HRMS (ESI) calculated [M+Na]+ for C20H20Na: 283.1457, found: 283.1473.

1-(Oct-1-yn-1-yl)-2-(1-phenylvinyl)benzene (1k): Yield: 73% (288 mg). Rf = 0.8 (petroleum ether/ethyl acetate 90:10). Physical aspect: yellow oil. 1

H NMR (400 MHz, CDCl3): δ = 7.43–7.37 (m, 1H, Ar–H), 7.30–7.21 (m, 8H, Ar–H), 5.72 (d, J

= 1.3 Hz, 1H, =CH), 5.34 (d, J = 1.3 Hz, 1H, =CH), 2.10 (t, J = 6.8 Hz, 2H, CH2), 1.30–1.16 (m, 8H, 4 × CH2), 0.86 (t, J = 7.0 Hz, 3H, CH3) ppm. 13C{1H} NMR (100 MHz, CDCl3): δ = 149.2 (Ar–C), 144.2 (Ar–C), 141.1 (Ar–C), 132.5 (Ar–CH), 129.9 (Ar–CH), 128.0 (2 × Ar–CH), 127.35 (Ar–CH), 127.29 (Ar–CH), 127.2 (Ar–CH), 126.9 (2 × Ar–CH), 123.4 (Ar–C), 115.7 (=CH2), 94.9 (C), 79.6 (C), 31.3 (CH2), 28.5 (CH2), 28.4 (CH2), 22.5 (CH2), 19.4 (CH2), 14.1 (CH3) ppm. HRMS (ESI) calculated [M+H]+ for C22H25: 289.1951, found: 289.1947.



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10-(2-(1-Phenylvinyl)phenyl)dec-9-yn-1-yl acetate (1l): Yield: 77% (377 mg). Rf = 0.6 (petroleum ether/ethyl acetate 90:10). Physical aspect: colourless oil. 1H NMR (400 MHz, CDCl3): δ = 7.44–7.39 (m, 1H, Ar–H), 7.30–7.22 (m, 8H, Ar–H), 5.72 (s, 1H, =CH), 5.34 (s, 1H, =CH), 4.05 (t, J = 6.7 Hz, 2H, OCH2), 2.11 (t, J = 6.6 Hz, 2H, CH2), 2.04 (s, 3H, CH3), 1.63–1.59 (m, 2H, CH2), 1.36–1.21 (m, 10H, 5 × CH2) ppm.

13

C{1H} NMR

(100 MHz, CDCl3): δ = 171.2 (C=O), 149.2 (Ar–C), 144.1 (Ar–C), 141.1 (Ar–C), 132.4 (Ar– CH), 129.9 (Ar–CH), 128.0 (2 × Ar–CH), 127.4 (Ar–CH), 127.3 (Ar–CH), 127.2 (Ar–CH), 126.9 (2 × Ar–CH), 123.3 (Ar–C), 115.7 (=CH2), 94.7 (C), 79.7 (C), 64.6 (OCH2), 29.1 (CH2), 29.0 (CH2), 28.6 (CH2), 28.6 (CH2), 28.3 (CH2), 25.7 (CH2), 21.0 (CH3), 19.3 (CH2) ppm. HRMS (ESI) calculated [M+Na]+ for C26H30O2Na: 397.2138, found: 397.2142.

10-(2-(1-Phenylvinyl)phenyl)dec-9-yn-1-ol (1m): Yield: 75% (249 mg). Rf = 0.3 (petroleum ether/ethyl acetate 90:10). Physical aspect: colourless oil. 1H NMR (400 MHz, CDCl3): δ = 7.45–7.38 (m, 1H, Ar–H), 7.32–7.19 (m, 8H, Ar–H), 5.72 (d, J = 1.2 Hz, 1H, =CH), 5.34 (d, J = 1.1 Hz, 1H, =CH), 3.62 (t, J = 6.6 Hz, 2H, OCH2), 2.11 (t, J = 6.7 Hz, 2H, CH2), 1.58–1.51 (m, 2H, CH2), 1.37–1.20 (m, 10H, 4 × CH2) ppm.

13

C{1H}

NMR (100 MHz, CDCl3): δ = 149.2 (Ar–C), 144.1(Ar–C), 141.0 (Ar–C), 132.4 (Ar–CH), 129.8 (Ar–CH), 128.0 (2 × Ar–CH), 127.34 (Ar–CH), 127.26 (Ar–CH), 127.2 (Ar–CH), 126.9 (2 × Ar– CH), 123.3 (Ar–C), 115.7 (=CH2), 94.7 (C), 79.7 (C), 63.0 (OCH2), 32.7 (CH2), 29.2 (CH2), 29.0 (CH2), 28.7 (CH2), 28.3 (CH2), 25.7 (CH2), 19.3 (CH2). HRMS (ESI) calculated [M+H]+ for C24H29O: 333.2213, found: 333.2219.


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1-(1-(3-Methoxyphenyl)vinyl)-2-(phenylethynyl)benzene (1n): Yield: 76% (236 mg). Rf = 0.7 (petroleum ether/ethyl acetate 90:10). Physical aspect: yellow oil. 1

H NMR (400 MHz, CDCl3): δ = 7.58–7.54 (m, 1H), 7.37–7.30 (m, 3H), 7.26–7.21 (m, 4H),

7.19–7.14 (m, 2H), 6.94–6.89 (m, 2H), 6.82 (ddd, J = 8.2, 2.6, 0.9 Hz, 1H), 5.78 (d, J = 1.2 Hz, 1H), 5.42 (d, J = 1.2 Hz, 1H), 3.75 (s, 3H) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 159.5

(Ar–C), 148.9 (Ar–C), 144.2 (Ar–C), 142.6 (Ar–C), 132.5 (Ar–CH), 131.4 (2 × Ar–CH), 130.0 (Ar–CH), 129.1 (Ar–CH), 128.2 (Ar–CH), 128.0 (2 × Ar–CH), 128.0 (Ar–CH), 127.4 (Ar–CH), 123.3 (Ar–C), 122.5 (Ar–C), 119.8 (Ar–CH), 116.4 (=CH2), 113.0 (Ar–CH), 112.9 (Ar–CH), 93.4 (C), 88.7 (C), 55.2 (OCH3) ppm. HRMS (ESI) calculated [M+H]+ for C23H19O: 311.1430, found: 311.1431.

1-(But-1-en-2-yl)-2-(phenylethynyl)benzene (1o): Yield: 81% (188 mg). Rf = 0.5 (petroleum ether/ethyl acetate 90:10). Physical aspect: yellow oil. 1

H NMR (400 MHz, CDCl3): δ = 7.53 (d, J = 7.3 Hz, 1H, Ar–CH), 7.50–7.45 (m, 2H, Ar–CH),

7.36–7.18 (m, 6H, Ar–CH), 5.24 (s, 1H, =CH), 5.10 (s, 1H, =CH), 2.60 (q, J = 7.4 Hz, 2H, CH2), 1.08 (t, J = 7.4 Hz, 3H, CH3) ppm. 13C{1H} NMR (100 MHz, CDCl3): δ = 151.2 (Ar–C), 146.0 (Ar–C), 132.4 (Ar–CH), 131.4 (2 × Ar–CH), 128.4 (Ar–CH), 128.3 (2 × Ar–CH), 128.1 (Ar– CH), 128.08 (Ar–CH), 126.7 (Ar–CH), 123.6 (Ar–C), 121.1 (Ar–C), 113.4 (=CH2), 92.3 (C), 89.0 (C), 29.7 (CH3), 12.7 (CH3) ppm. HRMS (ESI) calculated [M+H]+ for C18H17: 233.1325, found: 233.1322.

1-(Oct-1-yn-1-yl)-2-(prop-1-en-2-yl)benzene (1p):



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Yield: 69% (160 mg). Rf = 0.7 (petroleum ether/ethyl acetate 95:05). Physical aspect: yellow oil. 1

H NMR (400 MHz, CDCl3): δ = 7.39 (d, J = 7.5 Hz, 1H, Ar–H), 7.24–7.13 (m, 3H, Ar–H),

5.23–5.15 (m, 1H, =CH), 5.13–5.06 (m, 1H, =CH), 2.40 (t, J = 7.0 Hz, 2H, CH2), 2.17 (s, 3H, CH3), 1.62–1.54 (m, 2H, CH2), 1.49–1.41 (m, 2H, CH2), 1.35–1.28 (m, 4H, 2 × CH2), 0.90 (t, J = 6.9 Hz, 3H, CH3) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 145.9 (Ar–C), 145.4 (Ar–C),

132.8 (Ar–CH), 127.8 (Ar–CH), 127.4 (Ar–CH), 126.6 (Ar–CH), 121.6 (Ar–C), 115.3 (=CH2), 93.9 (C), 79.9 (C), 31.4 (CH2), 28.6 (CH2), 28.6 (CH2), 23.3 (CH3), 22.6 (CH2), 19.6 (CH2), 14.1 (CH3) ppm. HRMS (ESI) calculated [M+H]+ for C17H23: 227.1794, found: 227.1779.

1,2-Dimethoxy-4-((4-methoxyphenyl)ethynyl)-5-(1-phenylvinyl)benzene (1q): Yield: 83% (307 mg). Rf = 0.5 (petroleum ether/ethyl acetate 90:10). Physical aspect: yellow oil. 1

H NMR (400 MHz, CDCl3) δ 7.39–7.24 (m, 5H, Ar–H), 7.07–7.02 (m, 3H, Ar–H), 6.82 (s, 1H,

Ar–H), 6.77–6.71 (m, 2H, Ar–H), 5.75 (d, J = 1.2 Hz, 1H, =CH), 5.41 (d, J = 1.2 Hz, 1H, =CH), 3.92 (s, 3H, OCH3), 3.88 (s, 3H, OCH3), 3.76 (s, 3H, OCH3) ppm.

13

C{1H} NMR (100 MHz,

CDCl3): δ = 159.2 (Ar–C), 148.8 (2 × Ar–C), 148.0 (Ar–C), 141.0 (Ar–C), 137.4 (Ar–C), 132.6 (2 × Ar–CH), 128.1 (2 × Ar–CH), 127.4 (Ar–CH), 127.1 (2 × Ar–CH), 115.9 (=CH2), 115.6 (Ar– C), 114.9 (Ar–C), 114.6 (Ar–CH), 113.6 (2 × Ar–CH), 113.1 (Ar–CH), 92.1 (C), 87.5 (C), 56.0 (OCH3), 55.9 (OCH3), 55.2 (OCH3) ppm. HRMS (ESI) calculated [M+H]+ for C25H23O3: 371.1642, found: 371.1647.

5-(Phenylethynyl)-6-(1-phenylvinyl)benzo[d][1,3]dioxole (1r): Yield: 80% (259 mg). Rf = 0.6 (petroleum ether/ethyl acetate 90:10). Physical aspect: yellow oil. 1

H NMR (400 MHz, CDCl3): δ = 7.39–7.32 (m, 3H), 7.30–7.25 (m, 3H), 7.21–1.79 (m, 2H),


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7.11–7.08 (m, 2H), 6.99 (s, 1H), 6.80 (s, 1H), 5.99 (s, 2H), 5.74 (d, J = 1.1 Hz, 1H), 5.38 (d, J = 1.1 Hz, 1H) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 148.6 (Ar–C), 147.8 (Ar–C), 146.8

(Ar–C), 140.9 (Ar–C), 139.4 (Ar–C), 131.3 (2 × Ar–CH), 128.2 (2 × Ar–CH), 128.0 (2 × Ar– CH), 127.8 (Ar–CH), 127.5 (Ar–CH), 127.1 (2 × Ar–CH), 123.3 (Ar–C), 116.2 (=CH2), 115.7 (Ar–C), 111.9 (Ar–CH), 110.5 (Ar–CH), 101.5 (OCH2O), 92.1 (C), 88.8 (C) ppm. HRMS (ESI) calculated [M+H]+ for C23H17O2: 325.1223, found: 325.1238.

4-Fluoro-1-(phenylethynyl)-2-(1-phenylvinyl)benzene (1s): Yield: 83% (247 mg). Rf = 0.7 (petroleum ether/ethyl acetate 90:10). Physical aspect: yellow oil. 1

H NMR (400 MHz, CDCl3): δ = 7.52 (dd, J = 8.5, 5.8 Hz, 1H, Ar–H), 7.36–7.26 (m, 5H, Ar–H),

7.24–7.17 (m, 3H, Ar–H), 7.15–6.98 (m, 4H, Ar–H), 5.80 (s, 1H, =CH), 5.43 (s, 1H, =CH) ppm. 13

C{1H} NMR (100 MHz, CDCl3): δ = 161.2 (JC-F = 248.6 Hz, Ar–C), 148.1 (JC-F = 1.3 Hz, Ar–

C), 146.5 (JC-F = 7.9 Hz, Ar–C), 140.3 (Ar–C), 134.3 (JC-F = 8.4 Hz, Ar–CH), 131.4 (2 × Ar– CH), 128.3 (2 × Ar–CH), 128.0 (3 × Ar–CH), 127.7 (Ar–CH), 127.1 (2 × Ar–CH), 123.1 (Ar–C), 117.2 (JC-F = 22.1 Hz, Ar–CH), 116.8 (=CH2), 114.7 (JC-F = 21.7 Hz, Ar–CH), 93.1 (C), 87.7 (C) ppm. HRMS (ESI) calculated [M+H]+ for C22H16F: 299.1231, found: 299.1232.

1-(1-(3-Methoxyphenyl)prop-1-en-1-yl)-2-(phenylethynyl)benzene (1t): Yield: 86% (279 mg). Rf = 0.7 (petroleum ether/ethyl acetate 90:10). Physical aspect: yellow oil. Obtained as a ~3:1 mixture of isomers. NMR data for major isomer. 1H NMR (400 MHz, CDCl3): δ = 7.64–7.14 (m, 10H, Ar-H), 7.91–6.30 (m, 3H, Ar-H), 6.28–6.33 (m, 1H, =CH), 3.72 (s, 3H, OCH3), 1.70 (dd, J = 7.0, 1.7 Hz, 3H, CH3) ppm. 13C{1H} NMR (100 MHz, CDCl3): δ = 159.4 (C), 143.6 (C), 142.5 (C), 141.1 (C), 132.3 (CH), 131.5 (2 × CH), 130.4 (CH), 129.0 (CH),



128.14 (CH), 128.09 (2 × CH), 127.9 (CH), 127.0 (CH), 125.5 (CH), 123.5 (C), 123.4 (C), 119.4 (CH), 112.6 (CH), 111.8 (CH), 92.0 (C), 88.2 (C), 55.1 (OCH3), 15.7 (CH3) ppm. HRMS (ESI) calculated [M+H]+ for C24H21O: 325.1587, found: 325.1570.

1-(Phenylethynyl)-2-(prop-1-en-2-yl)benzene (1u):7b Yield: 81% (174 mg). Rf = 0.8 (petroleum ether/ethyl acetate 90:10). Physical aspect: yellow oil.

General Procedure (GP) for the Oxidative Coupling of ortho-(Alkynyl)styrenes with Allylic Alcohols. An oven-dried 10 mL Schlenk tube was charged with o-(alkyne)styrene 1 (0.3 mmol), allylic alcohol8-10 2 (0.9 mmol), PdCl2 (0.03 mmol), and 1,4-dioxane (1 mL) sequentially. The reaction mixture was heated in a 60 °C oil bath with rapid stirring for 24 hours under open-air atmosphere. After the reaction, the mixture was cooled to room temperature, diluted with ethyl acetate, and filtered through a short pad of celite. Evaporation of the solvent(s) under reduced pressure and purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate), furnished the desired polysubstituted naphthalene product 3.

Large Scale Synthesis of 3-(2,4-Diphenylnaphthalen-1-yl)-1-(4-ethylphenyl)propan-1-one (3aa): An oven-dried 10 mL Schlenk tube was charged with o-(alkyne)styrene 1a (1.4 g, 5 mmol), allylic alcohol 2a (2.43 g, 15 mmol), PdCl2 (89 mg, 0.5 mmol), and 1,4-dioxane (12 mL) sequentially. The reaction mixture was heated in a 60 °C oil bath with rapid stirring for 24 hours


Page 22 of 58

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under open-air atmosphere. After the reaction, the mixture was cooled to room temperature, diluted with ethyl acetate, and filtered through a short pad of celite. Evaporation of the solvent(s) under reduced pressure and purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate 90:10), furnished the desired product 3aa (1.65 g, 75%).

3-(2,4-Diphenylnaphthalen-1-yl)-1-(4-ethylphenyl)propan-1-one (3aa): GP was carried out with o-(alkyne)styrene 1a (84 mg, 0.3 mmol), alcohol 2a (146 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere. Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 95:5) furnished the naphthalene ketone 3aa (106 mg, 80%) as a pale yellow viscous liquid. TLC (petroleum ether/ethyl acetate 90:10): Rf(1a) = 0.7, Rf(3aa) = 0.5, UV detection. IR (MIR-ATR, 4000–600 cm-1): max = 2966, 2931, 1676, 1266, 733, 697 cm-1. 1H NMR (400 MHz, CDCl3): δ = 8.18 (d, J = 8.4 Hz, 1H, Ar–H), 8.00 (dd, J = 8.4, 0.8 Hz, 1H, Ar– H), 7.74–7.67 (m, 2H, Ar–H), 7.60–7.50 (m, 3H, Ar–H), 7.50–7.36 (m, 9H, Ar–H), 7.35 (s, 1H, Ar–H), 7.19 (d, J = 8.3 Hz, 2H, Ar–H), 3.5–3.47 (m, 2H, CH2), 3.28–3.19 (m, 2H, CH2), 2.67 (q, J = 7.6 Hz, 2H, CH2), 1.23 (t, J = 7.6 Hz, 3H, CH3) ppm. 13C{1H} NMR (100 MHz, CDCl3): δ = 198.9 (C=O), 150.0 (Ar–C), 142.2 (Ar–C), 140.5 (Ar–C), 139.2 (Ar–C), 138.5 (Ar–C), 134.2 (Ar–C), 133.7 (Ar–C), 132.0 (Ar–C), 131.4 (Ar–C), 130.2 (2 × Ar–CH), 129.4 (Ar–CH), 129.2 (2 × Ar–CH), 128.4 (2 × Ar–CH), 128.3 (2 × Ar–CH), 128.2 (2 × Ar–CH), 128.0 (2 × Ar–CH), 127.2 (Ar–CH), 127.1 (Ar–CH), 127.0 (Ar–CH), 126.5 (Ar–CH), 125.6 (Ar–CH), 124.4 (Ar– CH), 39.9 (CH2), 28.9 (CH2), 24.2 (CH2), 15.2 (CH3) ppm. HRMS (ESI) calculated [M+H]+ for C33H29O: 441.2213, found: 441.2215.



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1-(4-Ethylphenyl)-3-(4-phenyl-2-(m-tolyl)naphthalen-1-yl)propan-1-one (3ba): GP was carried out with o-(alkyne)styrene 1b (88 mg, 0.3 mmol), alcohol 2a (146 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere. Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 95:5) furnished the naphthalene ketone 3ba (99 mg, 73%) as a pale yellow viscous liquid. TLC (petroleum ether/ethyl acetate 90:10): Rf(1b) = 0.7, Rf(3ba) = 0.5, UV detection. IR (MIR-ATR, 4000–600 cm-1): max = 2966, 2928, 1676, 1266, 733, 699 cm -1. 1

H NMR (400 MHz, CDCl3): δ = 8.18 (d, J = 8.4 Hz, 1H, Ar–H), 7.99 (d, J = 8.4 Hz, 1H, Ar–H),

7.70 (dd, J = 8.2, 1.9 Hz, 2H, Ar–H), 7.57–7.50 (m, 3H, Ar–H), 7.47–7.28 (m, 6H, Ar–H), 7.21– 7.16 (m, 5H, Ar–H), 3.53–3.50 (m, 2H, CH2), 3.26–3.20 (m, 2H, CH2), 2.66 (q, J = 7.5 Hz, 2H, CH2), 2.38 (s, 3H, CH3), 1.22 (td, J = 7.5, 1.7 Hz, 3H, CH3) ppm.

13

C{1H} NMR (100 MHz,

CDCl3): δ = 199.0 (C=O), 149.9 (Ar–C), 142.2 (Ar–C), 140.6 (Ar–C), 139.3 (Ar–C), 138.5 (Ar– C), 137.9 (Ar–C), 134.3 (Ar–C), 133.6 (Ar–C), 132.0 (Ar–C), 131.4 (Ar–C), 130.1 (2 × Ar–CH), 130.0 (Ar–CH), 129.4 (Ar–CH), 128.3 (2 × Ar–CH), 128.2 (Ar–CH, Ar–C), 128.2 (2 × Ar–CH, Ar–C), 128.0 (2 × Ar–CH), 127.8 (Ar–CH), 127.2 (Ar–CH), 126.9 (Ar–CH), 126.5 (Ar–CH), 126.3 (Ar–CH), 125.5 (Ar–CH), 124.4 (Ar–CH), 40.0 (CH2), 28.9 (CH2), 24.3 (CH2), 21.5 (CH3), 15.2 (CH3) ppm. HRMS (ESI) calculated [M+H]+ for C34H31O: 455.2369, found: 455.2357.

1-(4-Ethylphenyl)-3-(4-phenyl-2-(p-tolyl)naphthalen-1-yl)propan-1-one (3ca): GP was carried out with o-(alkyne)styrene 1c (88 mg, 0.3 mmol), alcohol 2a (146 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere.


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Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 95:5) furnished the naphthalene ketone 3ca (102 mg, 75%) as a pale yellow viscous liquid. TLC (petroleum ether/ethyl acetate 90:10): Rf(1c) = 0.7, Rf(3ca) = 0.5, UV detection. IR (MIR-ATR, 4000–600 cm-1): max = 2966, 2928, 1676, 1266, 733, 699 cm-1. 1H NMR (400 MHz, CDCl3): δ = 8.17 (d, J = 8.5 Hz, 1H, Ar–H), 7.99 (d, J = 8.4 Hz, 1H, Ar–H), 7.71 (d, J = 8.2 Hz, 2H, Ar–H), 7.58–7.37 (m, 7H, Ar–H), 7.35 (s, 1H, Ar–H), 7.30 (d, J = 8.0 Hz, 2H, Ar–H), 7.23 (d, J = 7.8 Hz, 2H, Ar–H), 7.18 (d, J = 8.1 Hz, 2H, Ar–H), 3.55–3.49 (m, 2H, CH2), 3.26–3.20 (m, 2H, CH2), 2.67 (q, J = 7.6 Hz, 2H, CH2), 2.41 (s, 3H, CH3), 1.23 (t, J = 7.6 Hz, 3H, CH3) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 198.9 (C=O), 149.9 (Ar–C),

140.5 (Ar–C), 139.3 (Ar–C), 139.1 (Ar–C), 138.5 (Ar–C), 136.6 (Ar–C), 134.2 (Ar–C), 133.7 (Ar–C), 132.0 (Ar–C), 131.3 (Ar–C), 130.1 (2 × Ar–CH), 129.5 (Ar–CH), 129.1 (2 × Ar–CH), 129.0 (2 × Ar–CH), 128.3 (2 × Ar–CH), 128.2 (2 × Ar–CH), 128.0 (2 × Ar–CH), 127.2 (Ar– CH), 126.9 (Ar–CH), 126.5 (Ar–CH), 125.5 (Ar–CH), 124.3 (Ar–CH), 40.0 (CH2), 28.9 (CH2), 24.2 (CH2), 21.2 (CH3), 15.2 (CH3) ppm. HRMS (ESI) calculated [M+H]+ for C34H31O: 455.2369, found: 455.2377.

1-(4-Ethylphenyl)-3-(2-(4-methoxyphenyl)-4-phenylnaphthalen-1-yl)propan-1-one (3da): GP was carried out with o-(alkyne)styrene 1d (93 mg, 0.3 mmol), alcohol 2a (146 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere. Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 94:6) furnished the naphthalene ketone 3da (121 mg, 86%) as a white solid compound. TLC (petroleum ether/ethyl acetate 90:10): Rf(1d) = 0.6, Rf(3da) = 0.4, UV detection. IR (MIR-ATR, 4000–600 cm-1): max = 2963, 2930, 1676, 1243, 1176, 768 cm-1.



1

H NMR (400 MHz, CDCl3): δ = 8.17 (d, J = 8.5 Hz, 1H, Ar–H), 7.99 (dd, J = 8.5, 0.9 Hz, 1H,

Ar–H), 7.74–7.68 (m, 2H, Ar–H), 7.59–7.38 (m, 7H, Ar–H), 7.36–7.31 (m, 3H, Ar–H), 7.20 (d, J = 8.4 Hz, 2H, Ar–H), 7.00–6.94 (m, 2H, Ar–H), 3.85 (s, 3H, OCH3), 3.57–3.47 (m, 2H, CH2), 3.28–3.18 (m, 2H, CH2), 2.68 (q, J = 7.6 Hz, 2H, CH2), 1.24 (t, J = 7.6 Hz, 3H, CH3) ppm. C{1H} NMR (100 MHz, CDCl3): δ = 199.0 (C=O), 158.7 (Ar–C), 150.0 (Ar–C), 140.6 (Ar–C),

13

138.8 (Ar–C), 138.5 (Ar–C), 134.6 (Ar–C), 134.2 (Ar–C), 133.9 (Ar–C), 132.0 (Ar–C), 131.3 (Ar–C), 130.3 (2 × Ar–CH), 130.2 (2 × Ar–CH), 129.7 (Ar–CH), 128.3 (2 × Ar–CH), 128.2 (2 × Ar–CH), 128.0 (2 × Ar–CH), 127.2 (Ar–CH), 126.9 (Ar–CH), 126.5 (Ar–CH), 125.5 (Ar–CH), 124.4 (Ar–CH), 113.8 (2 × Ar–CH), 55.3 (OCH3), 39.9 (CH2), 28.9 (CH3), 24.2 (CH2), 15.2 (CH3) ppm. HRMS (ESI) calculated [M+H]+ for C34H31O2: 471.2319, found 471.2312.

1-(4-Ethylphenyl)-3-(2-(3-fluorophenyl)-4-phenylnaphthalen-1-yl)propan-1-one (3ea): GP was carried out with o-(alkyne)styrene 1e (89 mg, 0.3 mmol), alcohol 2a (146 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere. Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 96:4) furnished the naphthalene ketone 3ea (99 mg, 72%) as a pale yellow viscous liquid. TLC (petroleum ether/ethyl acetate 90:10): Rf(1e) = 0.7, Rf(3ea) = 0.6, UV detection. IR (MIR-ATR, 4000–600 cm-1): max = 2966, 2931, 1678, 1266, 768, 700 cm-1. 1H NMR (400 MHz, CDCl3): δ = 8.17 (d, J = 8.5 Hz, 1H, Ar–H), 8.00 (d, J = 7.9 Hz, 1H, Ar–H), 7.75 (d, J = 8.3 Hz, 2H, Ar–H), 7.62–7.52 (m, 1H, Ar–H), 7.53–7.36 (m, 7H, Ar–H), 7.31 (s, 1H, Ar–H), 7.25–7.16 (m, 3H, Ar–H), 7.15–7.04 (m, 2H, Ar–H), 3.56–3.45 (m, 2H, CH2), 3.30– 3.19 (m, 2H, CH2), 2.68 (q, J = 7.6 Hz, 2H, CH2), 1.24 (t, J = 7.6 Hz, 3H, CH3) ppm. 13C{1H} NMR (100 MHz, CDCl3): δ = 198.7 (C=O), 162.6 (d, JC,F = 245 Hz, Ar–C), 150.1 (Ar–C), 144.4


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(d, JC,F = 8 Hz, Ar–C), 140.3 (Ar–C), 138.8 (Ar–C), 137.9 (Ar–C), 134.2 (Ar–C), 133.8 (Ar–C), 131.9 (Ar–C), 131.6 (Ar–C), 130.1 (2 × Ar–CH), 129.9 (d, JC,F = 8 Hz, Ar–CH), 128.9 (Ar–CH), 128.3 (4 × Ar–CH), 128.1 (2 × Ar–CH), 127.3 (Ar–CH), 127.0 (Ar–CH), 126.7 (Ar–CH), 125.9 (Ar–CH), 125.1 (d, JC,F = 3 Hz, Ar–CH), 124.4 (Ar–CH), 116.4 (d, JC,F = 21 Hz, Ar–CH), 114.1 (d, JC,F = 21 Hz, Ar–CH), 39.8 (CH2), 28.9 (CH2), 24.1 (CH2), 15.2 (CH3) ppm. 19F NMR (376 MHz, CDCl3): δ = –112.91 (s, 1F) ppm. HRMS (ESI) calculated [M+H]+ for C33H28OF: 459.2119, found: 459.2107.

3-(2-(2-Chlorophenyl)-4-phenylnaphthalen-1-yl)-1-(4-ethylphenyl)propan-1-one (3fa): GP was carried out with o-(alkyne)styrene 1f (94 mg, 0.3 mmol), alcohol 2a (146 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere. Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 94:6) furnished the naphthalene ketone 3fa (98 mg, 69%) as a pale yellow viscous liquid. TLC (petroleum ether/ethyl acetate 90:10): Rf(1f) = 0.6, Rf(3fa) = 0.4, UV detection. IR (MIR-ATR, 4000–600 cm-1): max = 2967, 2932, 1677, 1265, 733, 698 cm-1. 1H NMR (400 MHz, CDCl3): δ = 8.18 (d, J = 8.5 Hz, 1H, Ar–H), 8.02 (d, J = 8.5 Hz, 1H, Ar–H), 7.71 (d, J = 8.1 Hz, 2H, Ar–H), 7.60–7.44 (m, 7H, Ar–H), 7.42–7.30 (m, 4H, Ar–H), 7.26 (s, 1H, Ar–H), 7.19 (d, J = 8.1 Hz, 2H, Ar–H), 3.46–3.13 (m, 4H, 2 × CH2), 2.66 (q, J = 7.6 Hz, 2H, CH2), 1.22 (t, J = 7.6 Hz, 3H, CH3) ppm. 13C{1H} NMR (100 MHz, CDCl3): δ = 198.9 (C=O), 150.0 (Ar–C), 140.6 (Ar–C), 140.4 (Ar–C), 138.7 (Ar–C), 136.3 (Ar–C), 134.4 (Ar–C), 134.2 (Ar–C), 133.4 (Ar–C), 131.9 (Ar–C), 131.7 (Ar–C), 131.2 (Ar–CH), 130.2 (2 × Ar–CH), 129.7 (Ar–CH), 128.9 (Ar–CH), 128.8 (Ar–CH), 128.3 (2 × Ar–CH), 128.2 (2 × Ar–CH), 128.0 (2 × Ar–CH), 127.2 (Ar–CH), 127.0 (Ar–CH), 126.8 (Ar–CH), 126.5 (Ar–CH), 125.9 (Ar–CH),



124.4 (Ar–CH), 39.3 (CH2), 28.9 (CH2), 24.5 (CH2), 15.2 (CH3) ppm. HRMS (ESI) calculated [M+H]+ for C33H28OCl: 475.1823, found: 475.1838.

1-(4-Ethylphenyl)-3-(2-(4-nitrophenyl)-4-phenylnaphthalen-1-yl)propan-1-one (3ga): GP was carried out with o-(alkyne)styrene 1g (97 mg, 0.3 mmol), alcohol 2a (146 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere. Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 97:3) furnished the naphthalene ketone 3ga (105 mg, 72%) as a pale yellow viscous liquid. TLC (petroleum ether/ethyl acetate 90:10): Rf(1g) = 0.5, Rf(3ga) = 0.4, UV detection. IR (MIR-ATR, 4000–600 cm-1): max = 2965, 1669, 1516, 1343, 722 cm-1. 1H NMR (400 MHz, CDCl3): δ = 8.32–8.25 (m, 2H, Ar–H), 8.17 (d, J = 8.4 Hz, 1H, Ar–H), 8.00 (dd, J = 8.4, 0.9 Hz, 1H, Ar–H), 7.77–7.71 (m, 2H, Ar–H), 7.64–7.55 (m, 3H, Ar–H), 7.53–7.42 (m, 6H, Ar–H), 7.27 (s, 1H, Ar–H), 7.21 (d, J = 8.4 Hz, 2H, Ar–H), 3.53–3.45 (m, 2H, CH2), 3.29–3.21 (m, 2H, CH2), 2.67 (q, J = 7.6 Hz, 2H, CH2), 1.23 (t, J = 7.6 Hz, 3H, CH3) ppm. 13C{1H} NMR (100 MHz, CDCl3): δ = 198.2 (C=O), 150.3 (Ar–C), 149.1 (Ar–C), 147.0 (Ar–C), 140.1 (Ar–C), 139.2 (Ar–C), 136.8 (Ar–C), 134.1 (Ar–C), 133.9 (Ar–C), 131.9 (Ar–C), 131.8 (Ar–C), 130.4 (2 × Ar–CH), 130.1 (2 × Ar–CH), 128.4 (2 × Ar–CH), 128.2 (2 × Ar–CH), 128.1 (Ar–CH), 128.07 (2 × Ar–CH), 127.5 (Ar–CH), 127.2 (Ar–CH), 127.0 (Ar–CH), 126.3 (Ar–CH), 124.4 (Ar–CH), 123.6 (2 × Ar–CH), 39.6 (CH2), 28.9 (CH2), 24.0 (CH2), 15.1 (CH3) ppm. HRMS (ESI) calculated [M+H]+ for C33H28NO3: 486.2064, found: 486.2072.

Methyl 4-(1-(3-(4-ethylphenyl)-3-oxopropyl)-4-phenylnaphthalen-2-yl)benzoate (3ha):


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GP was carried out with o-(alkyne)styrene 1h (101 mg, 0.3 mmol), alcohol 2a (146 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere. Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 94:6) furnished the naphthalene ketone 3ha (106 mg, 71%) as a pale yellow viscous liquid. TLC (petroleum ether/ethyl acetate 90:10): Rf(1h) = 0.6, Rf(3ha) = 0.4, UV detection. IR (MIR-ATR, 4000–600 cm-1): max = 2960, 1718, 1676, 1272, 1107, 709 cm-1. 1

H NMR (400 MHz, CDCl3): δ = 8.18 (d, J = 8.5 Hz, 1H, Ar–H), 8.14–8.09 (m, 2H, Ar–H), 8.00

(dd, J = 8.5, 0.9 Hz, 1H, Ar–H), 7.74–7.67 (m, 2H, Ar–H), 7.58 (ddd, J = 8.4, 6.8, 1.3 Hz, 1H, Ar–H), 7.52–7.41 (m, 8H, Ar–H), 7.31 (s, 1H, Ar–H), 7.18 (d, J = 8.4 Hz, 2H, Ar–H), 3.94 (s, 3H, OCH3), 3.56–3.43 (m, 2H, CH2), 3.28–3.19 (m, 2H, CH2), 2.66 (q, J = 7.7 Hz, 2H, CH2), 1.23 (t, J = 7.6 Hz, 3H, CH3) ppm. 13C{1H} NMR (100 MHz, CDCl3): δ = 198.5 (C=O), 166.8 (C=O), 150.0 (Ar–C), 147.0 (Ar–C), 140.3 (Ar–C), 138.8 (Ar–C), 138.0 (Ar–C), 134.1 (Ar–C), 133.7 (Ar–C), 131.9 (Ar–C), 131.6 (Ar–C), 130.1 (2 × Ar–CH), 129.6 (2 × Ar–CH), 129.4 (2 × Ar–CH), 128.9 (Ar–C), 128.6 (Ar–CH), 128.3 (2 × Ar–CH), 128.2 (2 × Ar–CH), 128.0 (2 × Ar– CH), 127.3 (Ar–CH), 127.0 (Ar–CH), 126.7 (Ar–CH), 125.9 (Ar–CH), 124.4 (Ar–CH), 52.1 (OCH3), 39.8 (CH2), 28.9 (CH2), 24.1(CH2), 15.09 (CH3) ppm. HRMS (ESI) calculated [M+H]+ for C35H31O3: 499.2268, found: 499.2277.

1-(4-Ethylphenyl)-3-(4-phenyl-2-(thiophen-3-yl)naphthalen-1-yl)propan-1-one (3ia): GP was carried out with o-(alkyne)styrene 1i (86 mg, 0.3 mmol), alcohol 2a (146 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere. Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 95:5) furnished the naphthalene ketone 3ia (88 mg, 66%) as a brown viscous



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liquid. TLC (petroleum ether/ethyl acetate 90:10): Rf(1i) = 0.7, Rf(3ia) = 0.5, UV detection. IR (MIR-ATR, 4000–600 cm-1): max = 2966, 2930, 1675, 1265, 732, 697 cm-1. 1H NMR (400 MHz, CDCl3): δ = 8.17 (d, J = 8.5 Hz, 1H, Ar–H), 7.97 (dd, J = 8.4, 0.8 Hz, 1H, Ar–H), 7.80–7.74 (m, 2H, Ar–H), 7.58–7.38 (m, 9H, Ar–H), 7.28 (dd, J = 3.0, 1.3 Hz, 1H, Ar–H), 7.25–7.21 (m, 2H, Ar–H), 7.19 (dd, J = 4.9, 1.3 Hz, 1H, Ar–H), 3.63–3.54 (m, 2H, CH2), 3.32–3.23 (m, 2H, CH2), 2.68 (q, J = 7.6 Hz, 2H, CH2), 1.24 (t, J = 7.6 Hz, 3H, CH3) ppm.

13

C{1H} NMR (100 MHz,

CDCl3): δ = 198.8 (C=O), 150.0 (Ar–C), 142.3 (Ar–C), 140.5 (Ar–C), 138.7 (Ar–C), 134.4 (Ar– C), 134.3 (Ar–C), 133.8 (Ar–C), 132.1 (Ar–C), 131.5 (Ar–C), 130.1 (2 × Ar–CH), 129.4 (Ar– CH), 129.1 (Ar–CH), 128.3 (2 × Ar–CH), 128.2 (2 × Ar–CH), 128.1 (2 × Ar–CH), 127.3 (Ar– CH), 127.0 (Ar–CH), 126.5 (Ar–CH), 125.7 (Ar–CH), 125.6 (Ar–CH), 124.4 (Ar–CH), 122.9 (Ar CH), 40.0 (CH2), 28.9 (CH2), 24.3 (CH2), 15.2 (CH3) ppm. HRMS (ESI) calculated [M+H]+ for C31H27OS: 447.1777, found: 447.1792.

3-(2-Butyl-4-phenylnaphthalen-1-yl)-1-(4-ethylphenyl)propan-1-one (3ja): GP was carried out with o-(alkyne)styrene 1j (78 mg, 0.3 mmol), alcohol 2a (146 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere. Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 96:4) furnished the naphthalene ketone 3ja (74 mg, 59%) as a brown viscous liquid. TLC (petroleum ether/ethyl acetate 90:10): Rf(1j) = 0.8, Rf(3ja) = 0.6, UV detection. IR (MIR-ATR, 4000–600 cm-1): max = 2958, 2925, 2858, 1679, 1178, 763, 699 cm-1. 1H NMR (400 MHz, CDCl3): δ = 8.07 (d, J = 8.6 Hz, 1H, Ar–H), 7.91 (d, J = 8.2 Hz, 3H, Ar–H), 7.52–7.45 (m, 5H, Ar–H), 7.44–7.39 (m, 1H, Ar–H), 7.39–7.34 (m, 1H, Ar–H), 7.28 (d, J = 3.3 Hz, 2H, Ar–H), 7.26 (s, 1H, Ar–H), 3.65–3.51 (m, 2H, CH2), 3.41–3.29 (m, 2H, CH2), 2.88–2.78 (m, 2H,


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CH2), 2.69 (q, J = 7.6 Hz, 2H, CH2), 1.72–1.62 (m, 2H, CH2), 1.48–1.39 (m, 2H, CH2), 1.25 (t, J = 7.6 Hz, 3H, CH3), 0.94 (t, J = 7.3 Hz, 3H, CH3) ppm. 13C{1H} NMR (100 MHz, CDCl3) δ = 199.1 (C=O), 150.1 (Ar–C), 140.9 (Ar–C), 138.7 (Ar–C), 137.7 (Ar–C), 134.5 (Ar–C), 133.3 (Ar–C), 132.3 (Ar–C), 130.7 (Ar–C), 130.1 (2 × Ar–CH), 129.5 (Ar–CH), 128.3 (2 × Ar–CH), 128.2 (2 × Ar–CH), 128.1 (2 × Ar–CH), 127.1 (Ar–CH), 126.8 (Ar–CH), 126.0 (Ar–CH), 124.8 (Ar–CH), 123.7 (Ar–CH), 39.5 (CH2), 34.0 (CH2), 33.6 (CH2), 28.9 (CH2), 22.9 (CH2), 22.5 (CH2), 15.2 (CH3), 14.0 (CH3) ppm. HRMS (ESI) calculated [M+H]+ for C31H33O: 421.2526, found: 421.2537.

1-(4-Ethylphenyl)-3-(2-hexyl-4-phenylnaphthalen-1-yl)propan-1-one (3ka): GP was carried out with o-(alkyne)styrene 1k (86 mg, 0.3 mmol), alcohol 2a (146 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere. Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 96:4) furnished the naphthalene ketone 3ka (75 mg, 56%) as a pale yellow viscous liquid. TLC (petroleum ether/ethyl acetate 90:10): Rf(1k) = 0.8, Rf(3ka) = 0.6, UV detection. IR (MIR-ATR, 4000–600 cm-1): max = 2958, 2925, 2858, 1676, 1178, 764, 699 cm-1. 1H NMR (400 MHz, CDCl3): δ = 8.07 (d, J = 8.6 Hz, 1H, Ar–H), 7.94–7.88 (m, 3H, Ar– H), 7.52–7.44 (m, 5H, Ar–H), 7.43–7.33 (m, 2H, Ar–H), 7.29–7.24 (m, 3H, Ar–H), 3.63–3.53 (m, 2H, CH2), 3.40–3.29 (m, 2H, CH2), 2.87–2.77 (m, 2H, CH2), 2.69 (q, J = 7.6 Hz, 2H, CH2), 1.73–1.63 (m, 2H, CH2), 1.46–1.38 (m, 2H, CH2), 1.32–1.19 (m, 7H, 2 × CH2, CH3), 0.86 (t, J = 5.9 Hz, 3H, CH3) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 198.9 (C=O), 150.0 (Ar–C),

140.9 (Ar–C), 138.7 (Ar–C), 137.6 (Ar–C), 134.5 (Ar–C), 133.27 (Ar–C), 132.30 (Ar–C), 130.7 (Ar–C), 130.1 (2 × Ar–CH), 129.4 (Ar–CH), 128.2 (2 × Ar–CH), 128.1 (2 × Ar–CH), 128.0 (2 ×



Ar–CH), 127.0 (Ar–CH), 126.8 (Ar–CH), 126.0 (Ar–CH), 124.7 (Ar–CH), 123.7 (Ar–CH), 39.5 (CH2), 33.8 (CH2), 31.8 (CH2), 31.7 (CH2), 29.5 (CH2), 28.8 (CH2), 22.6 (CH2), 22.4 (CH2), 15.1 (CH3), 14.0 (CH3) ppm. HRMS (ESI) calculated [M+H]+ for C33H37O: 449.2839, found: 449.2844.

8-(1-(3-(4-Ethylphenyl)-3-oxopropyl)-4-phenylnaphthalen-2-yl)octyl acetate (3la): GP was carried out with o-(alkyne)styrene 1l (112 mg, 0.3 mmol), alcohol 2a (146 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere. Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 94:6) furnished the naphthalene ketone 3la (106 mg, 66%) as a pale yellow viscous liquid. TLC (petroleum ether/ethyl acetate 90:10): Rf(1l) = 0.6, Rf(3la) = 0.4, UV detection. IR (MIR-ATR, 4000–600 cm-1): max = 2926, 2855, 1734, 1679, 1235, 765, 700 cm-1. 1

H NMR (400 MHz, CDCl3): δ = 8.07 (d, J = 8.6 Hz, 1H, Ar–H), 7.94–7.87 (m, 3H, Ar–H),

7.52–7.34 (m, 7H, Ar–H), 7.31–7.26 (m, 3H, Ar–H), 4.03 (t, J = 6.7 Hz, 2H, OCH2), 3.63–3.53 (m, 2H, CH2), 3.40–3.30 (m, 2H, CH2), 2.87–2.79 (m, 2H, CH2), 2.70 (q, J = 7.6 Hz, 2H, CH2), 2.02 (s, 3H, COCH3), 1.63–1.74 (m, 2H, CH2), 1.53–1.62 (m, 2H, CH2), 1.47–1.38 (m, 2H, CH2), 1.37–1.28 (m, 6H, 3 × CH2), 1.25 (t, J = 7.6 Hz, 3H, CH3) ppm. 13C{1H} NMR (100 MHz, CDCl3): δ = 199.1 (C=O), 171.2 (O–C=O), 150.1 (Ar–C), 140.9 (Ar–C), 138.7 (Ar–C), 137.6 (Ar–C), 134.5 (Ar–C), 133.3 (Ar–C), 132.3 (Ar–C), 130.7 (Ar–C), 130.1 (2 × Ar–CH), 129.5 (Ar–CH), 128.3 (2 × Ar–CH), 128.2 (2 × Ar–CH), 128.1 (2 × Ar–CH), 127.1 (Ar–CH), 126.8 (Ar–CH), 126.1 (Ar–CH), 124.8 (Ar–CH), 123.7 (Ar–CH), 64.6 (OCH2), 39.5 (CH2), 33.8 (CH2), 31.8 (CH2), 29.7 (CH2), 29.4 (CH2), 29.2 (CH2), 28.9 (CH2), 28.5 (CH2), 25.9 (CH2), 22.5


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(CH2), 20.9 (CH3), 15.2 (CH3) ppm. HRMS (ESI) calculated [M+H]+ for C37H43O3: 535.3207, found: 535.3185.

1-(4-Ethylphenyl)-3-(2-(8-hydroxyoctyl)-4-phenylnaphthalen-1-yl)propan-1-one (3ma): GP was carried out with o-(alkyne)styrene 1m (100 mg, 0.3 mmol), alcohol 2a (146 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere. Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 90:10) furnished the naphthalene ketone 3ma (100 mg, 68%) as a pale yellow viscous liquid. TLC (petroleum ether/ethyl acetate 90:10): Rf(1m) = 0.3, Rf(3ma) = 0.1, UV detection. IR (MIR-ATR, 4000–600 cm-1): max = 3411, 2926, 2855, 1676, 1267, 1179, 734, 699 cm-1. 1H NMR (400 MHz, CDCl3): δ = 8.07 (d, J = 8.5 Hz, 1H, Ar–H), 7.94–7.87 (m, 3H, Ar–H), 7.52–7.35 (m, 7H, Ar–H), 7.30–7.26 (m, 3H, Ar–H), 3.61 (t, J = 6.6 Hz, 2H, OCH2), 3.59–3.54 (m, 2H, CH2), 3.39–3.31 (m, 2H, CH2), 2.86–2.78 (m, 2H, CH2), 2.70 (q, J = 7.6 Hz, 2H, CH2), 1.73–1.63 (m, 2H, CH2), 1.58–1.49 (m, 2H, CH2), 1.46–1.38 (m, 2H, CH2), 1.37–1.29 (m, 6H, 3 × CH2), 1.25 (t, J = 7.6 Hz, 3H, CH3) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ =

199.2 (C=O), 150.2 (Ar–C), 140.9 (Ar–C), 138.7 (Ar–C), 137.6 (Ar–C), 134.5 (Ar–C), 133.3 (Ar–C), 132.3 (Ar–C), 130.7 (Ar–C), 130.1 (2 × Ar–CH), 129.5 (Ar–CH), 128.3 (2 × Ar–CH), 128.2 (2 × Ar–CH), 128.1 (2 × Ar–CH), 127.1 (Ar–CH), 126.8 (Ar–CH), 126.1 (Ar–CH), 124.8 (Ar–CH), 123.7 (Ar–CH), 63.0 (OCH2), 39.5 (CH2), 33.8 (CH2), 32.7 (CH2), 31.8 (CH2), 29.7 (CH2), 29.4 (CH2), 29.3 (CH2), 28.9 (CH2), 25.6 (CH2), 22.4 (CH2), 15.2 (CH3) ppm. HRMS (ESI) calculated [M+H]+ for C35H41O2: 493.3101, found: 493.3088.

1-(4-Ethylphenyl)-3-(4-(3-methoxyphenyl)-2-phenylnaphthalen-1-yl)propan-1-one (3na):



GP was carried out with o-(alkyne)styrene 1n (93 mg, 0.3 mmol), alcohol 2a (146 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere. Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 95:5) furnished the naphthalene ketone 3na (99 mg, 70%) as a brown viscous liquid. TLC (petroleum ether/ethyl acetate 90:10): Rf(1n) = 0.7, Rf(3na) = 0.5, UV detection. IR (MIR-ATR, 4000–600 cm-1): max = 2965, 2933, 1676, 1263, 732, 698 cm-1. 1H NMR (400 MHz, CDCl3): δ = 8.18 (d, J = 8.5 Hz, 1H, Ar–H), 8.02 (d, J = 8.4 Hz, 1H, Ar–H), 7.70 (d, J = 8.2 Hz, 2H, Ar–H), 7.56 (t, J = 7.6 Hz, 1H, Ar–H), 7.48–7.35 (m, 8H, Ar–H), 7.18 (d, J = 8.1 Hz, 2H, Ar–H), 7.12–7.05 (m, 2H, Ar–H), 6.98–6.93 (m, 1H, Ar–H), 3.82 (s, 3H. OCH3), 3.56 – 3.46 (m, 2H, CH2), 3.27–3.20 (m, 2H, CH2), 2.66 (q, J = 7.6 Hz, 2H, CH2), 1.22 (t, J = 7.6 Hz, 3H, CH3) ppm. 13C{1H} NMR (100 MHz, CDCl3): δ = 198.8 (C=O), 159.5 (Ar– C), 140.0 (Ar–C), 142.2 (Ar–C), 141.9 (Ar–C), 139.1 (Ar–C), 138.4 (Ar–C), 134.2 (Ar–C), 133.7 (Ar–C), 132.0 (Ar–C), 131.4 (Ar–C), 129.24 (2 × Ar–CH), 129.18 (2 × Ar–CH), 128.34 (2 × Ar–CH), 128.29 (2 × Ar–CH), 128.0 (2 × Ar–CH), 127.1 (Ar–CH), 127.0 (Ar–CH), 126.5 (Ar–CH), 125.6 (Ar–CH), 124.3 (Ar–CH), 122.7 (Ar–CH), 115.7 (Ar–CH), 112.9 (Ar–CH), 55.3 (OCH3), 39.9 (CH2), 28.9 (CH2), 24.2 (CH2), 15.2 (CH3) ppm. HRMS (ESI) calculated [M+H]+ for C34H31O2: 471.2319, found: 471.2320.

3-(4-Ethyl-2-phenylnaphthalen-1-yl)-1-(4-ethylphenyl)propan-1-one (3oa): GP was carried out with o-(alkyne)styrene 1o (70 mg, 0.3 mmol), alcohol 2a (146 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere. Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 96:4) furnished the naphthalene ketone 3oa (72 mg, 61%) as a pale yellow


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solid. TLC (petroleum ether/ethyl acetate 90:10): Rf(1o) = 0.5, Rf(3oa) = 0.6, UV detection. IR (MIR-ATR, 4000–600 cm-1): max = 2966, 2932, 2874, 1676, 1266, 734, 699 cm-1. 1H NMR (400 MHz, CDCl3): δ = 8.14 (d, J = 6.3 Hz, 2H, Ar–H), 7.67 (d, J = 7.3 Hz, 2H, Ar–H), 7.58–7.51 (m, 2H, Ar–H), 7.47–7.36 (m, 5H, Ar–H), 7.25 (s, 1H, Ar–H), 7.17 (d, J = 7.9 Hz, 2H, Ar–H), 3.48– 3.39 (m, 2H, CH2), 3.20–3.07 (m, 4H, 2 × CH2), 2.66 (q, J = 7.6 Hz, 2H, CH2), 1.39 (t, J = 7.5 Hz, 3H, CH3), 1.22 (t, J = 7.6 Hz, 3H, CH3) ppm. 13C{1H} NMR (100 MHz, CDCl3): δ = 199.0 (C=O), 149.9 (Ar–C), 142.7 (Ar–C), 139.3 (Ar–C), 138.3 (Ar–C), 134.2 (Ar–C), 132.2 (Ar–C), 131.9 (Ar–C), 131.6 (Ar–C), 129.2 (2 × Ar–CH), 128.31 (2 × Ar–CH), 128.28 (2 × Ar–CH), 128.0 (2 × Ar–CH), 127.4 (Ar–CH), 126.9 (Ar–CH), 126.2 (Ar–CH), 125.4 (Ar–CH), 124.8 (Ar–CH), 124.5 (Ar–CH), 40.1 (CH2), 28.9 (CH2), 25.8 (CH2), 24.1 (CH2), 15.2 (CH3), 14.9 (CH3) ppm. HRMS (ESI) calculated [M+H]+ for C29H29O: 393.2213, found: 393.2205.

1-(4-Ethylphenyl)-3-(2-hexyl-4-methylnaphthalen-1-yl)propan-1-one (3pa): GP was carried out with o-(alkyne)styrene 1p (68 mg, 0.3 mmol), alcohol 2a (146 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere. Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 98:2) furnished the naphthalene ketone 3pa (41 mg, 35%) as a Red viscous liquid. TLC (petroleum ether/ethyl acetate 95:05): Rf(1p) = 0.7, Rf(3pa) = 0.8, UV detection. IR (MIR-ATR, 4000–600 cm-1): max = 2923, 2857, 1680, 1455, 1179, 755 cm-1. 1H NMR (400 MHz, CDCl3): δ = 8.05–7.97 (m, 2H, Ar–H), 7.89 (d, J = 8.2 Hz, 2H, Ar–H), 7.52– 7.44 (m, 2H, Ar–H), 7.26 (d, J = 8.2 Hz, 2H, Ar–H), 7.18 (s, 1H, Ar–H), 3.53–3.47 (m, 2H, CH2), 3.31–3.25 (m, 2H, CH2), 2.77–2.68 (m, 4H, 2 × CH2), 2.66 (s, 3H, CH3), 1.69–1.59 (m, 2H, CH2), 1.44–1.38 (m, 2H, CH2), 1.33–1.22 (m, 7H, CH2, CH3), 0.87 (t, J = 7.6 Hz, 3H, CH3)



ppm.


13

(Ar–C), 132.4 (Ar–C), 132.1 (Ar–C), 131.8 (Ar–C), 131.7 (Ar–C), 129.3 (Ar–CH), 128.3 (2 × Ar–CH), 128.1 (2 × Ar–CH), 125.8 (Ar–CH), 124.8 (Ar–CH), 124.5 (Ar–CH), 124.0 (Ar–CH), 39.7 (CH2), 33.8 (CH2), 31.9 (CH2), 31.8 (CH2), 29.5 (CH2), 28.9 (CH2), 22.6 (CH2), 22.3 (CH2), 19.4 (CH3), 15.2 (CH3), 14.1 (CH3) ppm. HRMS (ESI) calculated [M+H]+ for C28H35O: 387.2682, found: 387.2687.

3-(6,7-Dimethoxy-2-(4-methoxyphenyl)-4-phenylnaphthalen-1-yl)-1-(4-ethylphenyl)propan-1one (3qa): GP was carried out with o-(alkyne)styrene 1q (111 mg, 0.3 mmol), alcohol 2a (146 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere. Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 90:10) furnished the naphthalene ketone 3qa (129 mg, 81%) as a pale yellow solid. TLC (petroleum ether/ethyl acetate 90:10): Rf(1q) = 0.5, Rf(3qa) = 0.2, UV detection. IR (MIR-ATR, 4000–600 cm-1): max = 2960, 2834, 1675, 1606, 1507, 1246, 834, 701 cm-1. 1H NMR (400 MHz, CDCl3): δ = 7.72 (d, J = 8.2 Hz, 2H, Ar–H), 7.56–7.52 (m, 2H, Ar– H), 7.50–7.43 (m, 3H, Ar–H), 7.42–7.38 (m, 1H, Ar–H), 7.37–7.31 (m, 3H, Ar–H), 7.23–7.19 (m, 3H, Ar–H), 6.98 (d, J = 8.6 Hz, 2H, Ar–H), 4.00 (s, 3H, OCH3), 3.86 (s, 3H, OCH3), 3.83 (s, 3H, OCH3), 3.49–3.43 (m, 2H, CH2), 3.26–3.17 (m, 2H, CH2), 2.68 (q, J = 7.6 Hz, 2H, CH2), 1.24 (t, J = 7.6 Hz, 3H, CH3) ppm. 13C{1H} NMR (100 MHz, CDCl3): δ = 199.3 (C=O), 158.6 (Ar–C), 150.1 (Ar–C), 149.7 (Ar–C), 148.9 (Ar–C), 141.0 (Ar–C), 137.4 (Ar–C), 137.0 (Ar–C), 134.8 (Ar–C), 134.1 (Ar–C), 132.5 (Ar–C), 130.4 (2 × Ar–CH), 129.9 (2 × Ar–CH), 128.33 (2 × Ar–CH), 128.31 (2 × Ar–CH), 128.2 (Ar–CH), 128.0 (2 × Ar–CH), 127.8 (Ar–C), 127.1 (Ar–


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CH), 126.9 (Ar–C), 113.7 (2 × Ar–CH), 105.6 (Ar–CH), 103.3 (Ar–CH), 55.9 (OCH3), 55.6 (OCH3), 55.2 (OCH3), 39.5 (CH2), 28.9 (CH2), 24.6 (CH2), 15.1 (CH3) ppm. HRMS (ESI) calculated [M+H]+ for C36H35O4: 531.2530, found: 531.2548.

3-(6,8-Diphenylnaphtho[2,3-d][1,3]dioxol-5-yl)-1-(4-ethylphenyl)propan-1-one (3ra): GP was carried out with o-(alkyne)styrene 1r (97 mg, 0.3 mmol), alcohol 2a (146 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere. Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 94:6) furnished the naphthalene ketone 3ra (107 mg, 74%) as a yellow solid. TLC (petroleum ether/ethyl acetate 90:10): Rf(1r) = 0.6, Rf(3ra) = 0.4, UV detection. IR (MIRATR, 4000–600 cm-1): max = 2964, 2923, 1676, 1461, 1235, 1037, 734, 698 cm-1. 1H NMR (400 MHz, CDCl3): δ = 7.70 (d, J = 8.2 Hz, 2H, Ar–H), 7.50–7.37 (m, 12H, Ar–H), 7.27 (s, 1H, Ar– H), 7.21–7.18 (m, 2H, Ar–H), 6.03 (s, 2H, OCH2O), 3.42–3.36 (m, 2H, CH2), 3.22–3.16 (m, 2H, CH2), 2.68 (q, J = 7.6 Hz, 2H, CH2), 1.24 (t, J = 7.6 Hz, 3H, CH3) ppm.

13

C{1H} NMR (100

MHz, CDCl3): δ = 198.9 (C=O), 150.0 (Ar–C), 148.3 (Ar–C), 147.4 (Ar–C), 142.3 (Ar–C), 140.9 (Ar–C), 138.1 (Ar–C), 137.8 (Ar–C), 134.2 (Ar–C), 132.8 (Ar–C), 130.0 (2 × Ar–CH), 129.3 (2 × Ar–CH), 129.2 (Ar–C), 128.5 (Ar–C), 128.3 (6C, Ar–CH), 128.1 (Ar–CH), 128.0 (2 × Ar–CH), 127.2 (Ar–CH), 127.0 (Ar–CH), 103.2 (Ar–CH), 101.2(O-CH2-O), 100.9 (Ar–CH), 39.7 (CH2), 28.9 (CH2), 24.7 (CH2), 15.2 (CH3) ppm. HRMS (ESI) calculated [M+H]+ for C34H29O3: 485.2111, found: 485.2123.

1-(4-Ethylphenyl)-3-(6-fluoro-2,4-diphenylnaphthalen-1-yl)propan-1-one (3sa):



GP was carried out with o-(alkyne)styrene 1s (89 mg, 0.3 mmol), alcohol 2a (146 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere. Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 95:5) furnished the naphthalene ketone 3sa (92 mg, 67%) as a pale yellow solid. TLC (petroleum ether/ethyl acetate 90:10): Rf(1s) = 0.7, Rf(3sa) = 0.5, UV detection. IR (MIRATR, 4000–600 cm-1): max = 2967, 2932, 1677, 1262, 734, 699 cm-1. 1H NMR (400 MHz, CDCl3): δ = 8.18 (dd, J = 9.4, 5.6 Hz, 1H, Ar–H), 7.70 (d, J = 8.2 Hz, 2H, Ar–H), 7.61 (dd, J = 11.0, 2.6 Hz, 1H, Ar–H), 7.51–7.30 (m, 12H, Ar–H), 7.19 (d, J = 8.3 Hz, 2H, Ar–H), 3.55–3.45 (m, 2H, CH2), 3.26–3.15 (m, 2H, CH2), 2.66 (q, J = 7.6 Hz, 2H, CH2), 1.23 (t, J = 7.6 Hz, 3H, CH3) ppm. 13C{1H} NMR (100 MHz, CDCl3): δ = 198.7 (C=O), 161.6 (d, JC,F = 145 Hz, Ar–C), 150.1 (Ar–C), 141.9 (Ar–C), 140.0 (Ar–C), 138.5 (d, JC,F = 2 Hz, Ar–C), 138.0 (d, JC,F = 5 Hz, Ar–C), 134.1 (Ar–C), 133.9 (Ar–C), 132.6 (d, JC,F = 9 Hz, Ar–C), 130.4 (Ar–CH), 129.9 (2 × Ar–CH), 129.2 (2 × Ar–CH), 129.0 (Ar–C), 128.4 (4 × Ar–CH), 128.3 (2 × Ar–CH), 128.0 (2 × Ar–CH), 127.5 (Ar–CH), 127.2 (Ar–CH), 127.0 (d, JC,F = 9 Hz, Ar–CH), 116.5 (d, JC,F= 25 Hz, Ar–CH)), 110.3 (d, JC,F= 21 Hz, Ar–CH), 39.9 (CH2), 28.9 (CH2), 24.4 (CH2), 15.2 (CH3) ppm. 19

F NMR (376 MHz, CDCl3): δ = –114.59 (d, J = 9.02 Hz, 1F) ppm. HRMS (ESI) calculated

[M+H]+ for C33H28OF: 459.2119, found: 459.2122.

1-(4-Ethylphenyl)-3-(4-(3-methoxyphenyl)-3-methyl-2-phenylnaphthalen-1-yl)propan-1-one (3ta): GP was carried out with o-(alkyne)styrene 1t (97 mg, 0.3 mmol), alcohol 2a (146 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere. Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl


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acetate, 100:0 to 95:5) furnished the naphthalene ketone 3ta (93 mg, 64%) as a pale yellow liquid. TLC (petroleum ether/ethyl acetate 90:10): Rf(1t) = 0.7, Rf(3ta) = 0.5, UV detection. IR (MIR-ATR, 4000–600 cm-1): max = 2962, 2929, 1676, 1247, 763, 703 cm-1. 1H NMR (400 MHz, CDCl3): δ = 8.10 (d, J = 8.8 Hz, 1H, Ar–H), 7.66 (d, J = 7.9 Hz, 2H, Ar–H), 7.51–7.45 (m, 4H, Ar–H), 7.44–7.33 (m, 3H, Ar–H), 7.29 (d, J = 7.2 Hz, 2H, Ar–H), 7.19 (d, J = 8.0 Hz, 2H, Ar– H), 6.98 (dd, J = 7.9, 2.2 Hz, 1H, Ar–H, Ar–H), 6.90 (d, J = 7.5 Hz, 1H, Ar–H), 6.87–6.85 (m, 1H, Ar–H), 3.83 (s, 3H, OCH3), 3.32–3.26 (m, 2H, CH2), 3.21–3.14 (m, 2H, CH2), 2.68 (q, J = 7.6 Hz, 2H, CH2), 1.85 (s, 3H, CH3), 1.24 (t, J = 7.6 Hz, 3H, CH3) ppm.

13

C{1H} NMR (100

MHz, CDCl3): δ = 199.1 (C=O), 159.7 (Ar–C), 149.9 (Ar–C), 141.9 (Ar–C), 141.6 (Ar–C), 140.5 (Ar–C), 137.3 (Ar–C), 134.2 (Ar–C), 134.0 (Ar–C), 132.7 (Ar–C), 132.1 (Ar–C), 129.8 (Ar–C), 129.4 (Ar–CH), 129.1 (2 × Ar–CH), 128.7 (2 × Ar–CH), 128.3 (2 × Ar–CH), 128.0 (2 × Ar–CH), 127.3 (Ar–CH), 127.0 (Ar–CH), 125.6 (Ar–CH), 125.5 (Ar–CH), 123.8 (Ar–CH), 122.7 (Ar–CH), 115.7 (Ar–CH), 112.6 (Ar–CH), 55.2 (OCH3), 39.8 (CH2), 28.9 (CH2), 25.3 (CH2), 19.8 (CH3), 15.2 (CH3) ppm. HRMS (ESI) calculated [M+H]+ for C35H33O2: 485.2475, found: 485.2475.

3-(2,4-Diphenylnaphthalen-1-yl)-1-phenylpropan-1-one (3ab): GP was carried out with o-(alkyne)styrene 1a (84 mg, 0.3 mmol), alcohol 2b (121 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere. Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 95:5) furnished the naphthalene ketone 3ab (93 mg, 75%) as a pale yellow viscous liquid. TLC (petroleum ether/ethyl acetate 90:10): Rf(1a) = 0.7, Rf(3ab) = 0.5, UV detection. IR (MIR-ATR, 4000–600 cm-1): max = 3052, 1675, 1261, 732, 697 cm-1. 1H NMR



Page 40 of 58

(400 MHz, CDCl3): δ = 8.18 (d, J = 8.4 Hz, 1H, Ar–H), 8.00 (dd, J = 8.5, 0.8 Hz, 1H, Ar–H), 7.80–7.74 (m, 2H, Ar–H), 7.60–7.56 (m, 1H, Ar–H), 7.54–7.37 (m, 14H, Ar–H), 7.35 (s, 1H, Ar–H), 3.58–3.47 (m, 2H, CH2), 3.30–3.20 (m, 2H, CH2) ppm.

13

C{1H} NMR (100 MHz,

CDCl3): δ = 199.24 (C=O), 142.2 (Ar–C), 140.5 (Ar–C), 139.2 (Ar–C), 138.6 (Ar–C), 136.5 (Ar–C), 133.5 (Ar–C), 133.0 (Ar–CH), 132.0 (Ar–C), 131.4 (Ar–C), 130.2 (2 × Ar–CH), 129.4 (Ar–CH), 129.3 (2 × Ar–CH), 128.5 (2 × Ar–CH), 128.4 (2 × Ar–CH), 128.2 (2 × Ar–CH), 128.1 (2 × Ar–CH), 127.3 (Ar–CH), 127.1 (Ar–CH), 127.0 (Ar–CH), 126.6 (Ar–CH), 125.7 (Ar–CH), 124.3 (Ar–CH), 40.0 (CH2), 24.2 (CH2) ppm. HRMS (ESI) calculated [M+H]+ for C31H25O: 413.1900, found: 413.1902.

3-(4-Methyl-2-phenylnaphthalen-1-yl)-1-phenylpropan-1-one (3ub): GP was carried out with o-(alkyne)styrene 1u (65 mg, 0.3 mmol), alcohol 2b (121 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere. Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 96:4) furnished the naphthalene ketone 3ub (66 mg, 63%) as a pale yellow viscous liquid/semi-solid. TLC (petroleum ether/ethyl acetate 90:10): Rf(1u) = 0.8, Rf(3ub) = 0.6, UV detection. IR (MIR-ATR, 4000–600 cm-1): max = 2962, 1672, 1264, 739, 693 cm-1. 1H NMR (400 MHz, CDCl3): δ = 8.15–8.11 (m, 1H, Ar–H), 8.10–8.05 (m, 1H, Ar–H), 7.74 (dd, J = 8.3, 1.1 Hz, 2H, Ar–H), 7.61–7.55 (m, 2H, Ar–H), 7.53–7.45 (m, 1H, Ar–H), 7.43 (d, J = 7.5 Hz, 2H, Ar–H), 7.41–7.33 (m, 5H, Ar–H), 7.24 (s, 1H, Ar–H), 3.47–3.41 (m, 2H, CH2), 3.22–3.14 (m, 2H, CH2), 2.70 (s, 3H, CH3) ppm. 13C{1H} NMR (100 MHz, CDCl3): δ = 199.3 (C=O), 142.5 (Ar–C), 139.3 (Ar–C), 136.4 (Ar–C), 133.0 (Ar–CH), 132.4 (2 × Ar–C), 132.1 (Ar–C), 131.7 (Ar–C), 129.2 (2 × Ar–CH), 129.1 (Ar–CH), 128.5 (2 × Ar–CH), 128.3 (2 ×


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Ar–CH), 128.1 (2 × Ar–CH), 127.0 (Ar–CH), 126.4 (Ar–CH), 125.5 (Ar–CH), 125.0 (Ar–CH), 124.6 (Ar–CH), 40.2 (CH2), 24.0 (CH2), 19.3 (CH3) ppm. HRMS (ESI) calculated [M+H]+ for C26H23O: 351.1743, found: 351.1742.

3-(2,4-Diphenylnaphthalen-1-yl)-1-(naphthalen-1-yl)propan-1-one (3ac): GP was carried out with o-(alkyne)styrene 1a (84 mg, 0.3 mmol), alcohol 2c (166 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere. Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 95:5) furnished the naphthalene ketone 3ac (100 mg, 72%) as a pale yellow viscous liquid. TLC (petroleum ether/ethyl acetate 90:10): Rf(1a) = 0.7, Rf(3ac) = 0.5, UV detection. IR (MIR-ATR, 4000–600 cm-1): max=3052, 1675, 1262, 733, 697 cm-1. 1H NMR (400 MHz, CDCl3): δ = 8.61 (dd, J = 8.5, 3.0 Hz, 1H, Ar–H), 8.23 (dd, J = 8.5, 2.2 Hz, 1H, Ar–H), 7.99 (dd, J = 8.4, 2.4 Hz, 1H, Ar–H), 7.90 (d, J = 8.2 Hz, 1H, Ar–H), 7.82 (d, J = 8.1 Hz, 1H, Ar–H), 7.57–7.33 (m, 17H, Ar–H), 3.63–3.55 (m, 2H, CH2), 3.37–3.29 (m, 2H, CH2) ppm. C{1H} NMR (100 MHz, CDCl3): δ = 203.3 (C=O), 142.2, 140.5 (Ar–C), 139.2 (Ar–C), 138.6

13

(Ar–C), 135.2 (Ar–C), 133.9 (Ar–C), 133.5 (Ar–C), 132.7 (Ar–CH), 132.0 (Ar–C), 131.4 (Ar– C), 130.2 (Ar–C), 130.2 (2 × Ar–CH), 129.35 (Ar–CH), 129.25 (2 × Ar–CH), 128.4 (Ar–CH), 128.3 (2 × Ar–CH), 128.2 (2 ×Ar–CH), 127.9 (Ar–CH), 127.7 (Ar–CH), 127.2 (Ar–CH), 127.1 (Ar–CH), 127.0 (Ar–CH), 126.6 (Ar–CH), 126.4 (Ar–CH), 125.8 (Ar–CH), 125.7 (Ar–CH), 124.3 (2 × Ar–CH), 43.3 (CH2), 24.6 (CH2) ppm. HRMS (ESI) calculated [M+H]+ for C35H27O: 463.2056, found: 463.2065.

3-(2-Butyl-4-phenylnaphthalen-1-yl)-1-(3,4,5-trimethoxyphenyl)propan-1-one (3jd):



GP was carried out with o-(alkyne)styrene 1j (78 mg, 0.3 mmol), alcohol 2d (202 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere. Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 90:10) furnished the naphthalene ketone 3jd (88 mg, 61%) as a pale yellow viscous liquid. TLC (petroleum ether/ethyl acetate 90:10): Rf(1j) = 0.8, Rf(3jd) = 0.2, UV detection. IR (MIR-ATR, 4000–600 cm-1): max = 2935, 2867, 1676, 1583, 1457, 1412, 1324, 1123, 733, 698 cm-1. 1H NMR (400 MHz, CDCl3): δ = 8.09 (d, J = 8.5 Hz, 1H, Ar–H), 7.92 (d, J = 8.5 Hz, 1H, Ar–H), 7.53–7.45 (m, 5H, Ar–H), 7.43–7.35 (m, 2H, Ar–H), 7.30 (s, 1H, Ar–H), 7.22 (s, 2H, Ar–H), 3.91 (s, 3H, OCH3), 3.85 (s, 6H, 2 × OCH3), 3.60 (t, J = 8.4 Hz, 2H, CH2), 3.35 (t, J = 8.4 Hz, 2H, CH2), 2.83 (t, J = 8.0 Hz 2H, CH2), 1.72–1.63 (m, 2H, CH2), 1.51–1.39 (m, 2H, CH2), 0.95 (t, J = 7.3 Hz, 3H, CH3) ppm. 13C{1H} NMR (100 MHz, CDCl3): δ = 198.2 (C=O), 153.0 (2 × Ar–C), 142.6 (Ar–C), 140.8 (Ar–C), 138.8 (Ar–C), 137.7 (Ar–C), 133.1 (Ar– C), 132.3 (Ar–C), 132.0 (Ar–C), 130.7 (Ar–C), 130.0 (2 × Ar–CH), 129.5 (Ar–CH), 128.2 (2 × Ar–CH), 127.1 (Ar–CH), 126.8 (Ar–CH), 126.1 (Ar–CH), 124.8 (Ar–CH), 123.6 (Ar–CH), 105.5 (2 × Ar–CH), 60.8 (OCH3), 56.2 (2 × OCH3), 39.2 (CH2), 33.9 (CH2), 33.5 (CH2), 22.8 (CH2), 22.7 (CH2), 14.0 (CH3) ppm. HRMS (ESI) calculated [M+H]+ for C32H35O4: 483.2530, found: 483.2542.

1-(3,4-Dimethoxyphenyl)-3-(2,4-diphenylnaphthalen-1-yl)propan-1-one (3ae): GP was carried out with o-(alkyne)styrene 1a (84 mg, 0.3 mmol), alcohol 2e (175 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere. Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 90:10) furnished the naphthalene ketone 3ae (92 mg, 65%) as a pale yellow


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viscous liquid. TLC (petroleum ether/ethyl acetate 90:10): Rf(1a) = 0.7, Rf(3ae) = 0.2, UV detection. IR (MIR-ATR, 4000–600 cm-1): max = 2961, 2837, 1669, 1588, 1510, 1263, 1151, 1022, 762, 700 cm-1. 1H NMR (400 MHz, CDCl3): δ = 8.19 (d, J = 8.5 Hz, 1H, Ar–H), 8.00 (d, J = 8.3 Hz, 1H, Ar–H), 7.58 (t, J = 7.2 Hz, 1H, Ar–H), 7.54–7.37 (m, 12H, Ar–H), 7.35 (s, 1H, Ar–H), 7.29 (dd, J = 8.4, 1.8 Hz, 1H, Ar–H), 6.75 (d, J = 8.4 Hz, 1H, Ar–H), 3.92 (s, 3H, OCH3), 3.89 (s, 3H, OCH3), 3.55–3.49 (m, 2H, CH2), 3.25–3.19 (m, 2H, CH2) ppm.

13

C{1H}

NMR (100 MHz, CDCl3): δ = 197.9 (C=O), 153.2 (Ar–C), 149.0 (Ar–C), 142.3 (Ar–C), 140.5 (Ar–C), 139.2 (Ar–C), 138.6 (Ar–C), 133.7 (Ar–C), 132.0 (Ar–C), 131.4 (Ar–C), 130.2 (2 × Ar– CH), 129.8 (Ar–C), 129.4 (Ar–CH), 129.3 (2 × Ar–CH), 128.3 (2 × Ar–CH), 128.2 (2 × Ar–CH), 127.3 (Ar–CH), 127.1 (Ar–CH), 127.0 (Ar–CH), 126.5 (Ar–CH), 125.7 (Ar–CH), 124.4 (Ar– CH), 122.7 (Ar–CH), 110.1 (Ar–CH), 110.0 (Ar–CH), 56.03 (OCH3), 55.98 (OCH3), 39.5 (CH2), 24.4 (CH2) ppm. HRMS (ESI) calculated [M+H]+ for C33H29O3: 473.2111, found: 473.2114.

1-(Benzo[d][1,3]dioxol-5-yl)-3-(2-butyl-4-phenylnaphthalen-1-yl)propan-1-one (3jf): GP was carried out with o-(alkyne)styrene 1j (78 mg, 0.3 mmol), alcohol 2f (160 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere. Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 95:5) furnished the naphthalene ketone 3jf (77 mg, 59%) as a brown viscous liquid. TLC (petroleum ether/ethyl acetate 90:10): Rf(1j) = 0.8, Rf(3jf) = 0.5, UV detection. IR (MIR-ATR, 4000–600 cm-1): max = 2955, 2865, 1675, 1441, 1247, 1036, 735, 700 cm-1. 1H NMR (400 MHz, CDCl3) δ = 8.06 (d, J = 8.5 Hz, 1H, Ar–H), 7.90 (d, J = 7.8 Hz, 1H, Ar–H), 7.55 (dd, J = 8.2, 1.7 Hz, 1H, Ar–H), 7.50–7.35 (m, 8H, Ar–H), 7.28 (s, 1H, Ar–H), 6.81 (d, J = 8.2 Hz, 1H, Ar–H), 6.03 (s, 2H, OCH2O), 3.59–3.53 (m, 2H, CH2), 3.34–3.22 (m, 2H, CH2),



2.89–2.77 (m, 2H, CH2), 1.72–1.62 (m, 2H, CH2), 1.49 – 1.41 (m, 2H, CH2), 0.94 (t, J = 7.3 Hz, 3H, CH3) ppm. 13C{1H} NMR (100 MHz, CDCl3) δ = 197.5 (C=O), 151.8 (Ar–C), 148.2 (Ar– C), 140.9 (Ar–C), 138.7 (Ar–C), 137.7 (Ar–C), 133.2 (Ar–C), 132.3 (Ar–C), 131.7 (Ar–C), 130.7 (Ar–C), 130.1 (2 × Ar–CH), 129.5 (Ar–CH), 128.2 (2 × Ar–CH), 127.1 (Ar–CH), 126.8 (Ar–CH), 126.1 (Ar–CH), 124.8 (Ar–CH), 124.2 (Ar–CH), 123.7 (Ar–CH), 107.8 (2 × Ar–CH), 101.8 (OCH2O), 39.3 (CH2), 34.0 (CH2), 33.6 (CH2), 22.9 (CH2), 22.6 (CH2), 14.0 (CH3) ppm. HRMS (ESI) calculated [M+H]+ for C30H29O3: 437.2111, found: 437.2117.

1-(3-Bromophenyl)-3-(2,4-diphenylnaphthalen-1-yl)propan-1-one (3ag): GP was carried out with o-(alkyne)styrene 1a (84 mg, 0.3 mmol), alcohol 2g (190 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere. Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 96:4) furnished the naphthalene ketone 3ag (69 mg, 47%) as a pale yellow viscous liquid. TLC (petroleum ether/ethyl acetate 90:10): Rf(1a) = 0.7, Rf(3ag) = 0.6, UV detection. IR (MIR-ATR, 4000–600 cm-1): max = 3058, 1684, 1262, 1195, 734, 695 cm-1. 1H NMR (400 MHz, CDCl3): δ = 8.14 (d, J = 8.5 Hz, 1H, Ar–H), 8.00 (d, J = 8.5 Hz, 1H, Ar–H), 7.97 (t, J = 1.6 Hz, 1H, Ar–H), 7.64–7.55 (m, 3H, Ar–H), 7.53–7.36 (m, 11H, Ar–H), 7.34 (s, 1H, Ar–H), 7.22 (t, J = 7.9 Hz, 1H, Ar–H), 3.55–3.47 (m, 2H, CH2), 3.24–3.18 (m, 2H, CH2) ppm.

13


(Ar–C), 138.7 (Ar–C), 138.2 (Ar–C), 135.9 (Ar–CH), 133.2 (Ar–C), 131.9 (Ar–C), 131.4 (Ar– C), 131.1 (Ar–CH), 130.14 (2 × Ar–CH), 130.12 (Ar–CH), 129.4 (Ar–CH), 129.2 (2 × Ar–CH), 128.4 (2 × Ar–CH), 128.2 (2 × Ar–CH), 127.3 (Ar–CH), 127.2 (Ar–CH), 127.1 (Ar–CH), 126.62


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(Ar–CH), 126.57 (Ar–CH), 125.7 (Ar–CH), 124.2 (Ar–CH), 122.9 (Ar–C), 40.0 (CH2), 23.9 (CH2) ppm. HRMS (ESI) calculated [M+Na]+ for C31H23OBrNa: 513.0824, found: 513.0817.

1-(3-Chlorophenyl)-3-(4-(3-methoxyphenyl)-2-phenylnaphthalen-1-yl)propan-1-one (3nh): GP was carried out with o-(alkyne)styrene 1n (93 mg, 0.3 mmol), alcohol 2h (151 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere. Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 97:3) furnished the naphthalene ketone 3nh (59 mg, 41%) as a pale yellow viscous liquid. TLC (petroleum ether/ethyl acetate 90:10): Rf(1n) = 0.7, Rf(3nh) = 0.5, UV detection. IR (MIR-ATR, 4000–600 cm-1): max = 3060, 2957, 1685, 1260, 1042, 734, 698 cm-1. 1H NMR (400 MHz, CDCl3): δ = 8.14 (d, J = 8.5 Hz, 1H, Ar–H), 8.03 (d, J = 8.4 Hz, 1H, Ar–H), 7.81 (t, J = 1.8 Hz, 1H, Ar–H), 7.62–7.55 (m, 2H, Ar–H), 7.50–7.36 (m, 8H, Ar–H), 7.35 (s, 1H, Ar–H), 7.30 (t, J = 7.9 Hz, 1H, Ar–H), 7.13–7.09 (m, 1H, Ar–H), 7.08–7.05 (m, 1H, Ar– H), 6.99–6.95 (m, 1H, Ar–H), 3.84 (s, 3H, OCH3), 3.55–3.47 (m, 2H, CH2), 3.26–3.18 (m, 2H, CH2) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 197.9 (C=O), 159.5 (Ar–C), 142.1 (Ar–C),

141.9 (Ar–C), 139.2 (Ar–C), 138.6 (Ar–C), 138.0 (Ar–C), 134.9 (Ar–C), 133.2 (Ar–C), 132.9 (Ar–CH), 131.9 (Ar–C), 131.4 (Ar–C), 129.9 (Ar–CH), 129.2 (4 × Ar–CH), 128.4 (2 × Ar–CH), 128.2 (Ar–CH), 127.2 (Ar–CH), 127.1 (Ar–CH), 126.6 (Ar–CH), 126.1 (Ar–CH), 125.7 (Ar– CH), 124.2 (Ar–CH), 122.7 (Ar–CH), 115.7(Ar–CH), 112.9 (Ar–CH), 55.3 (OCH3), 40.0 (CH2), 23.9 (CH2) ppm. HRMS (ESI) calculated [M+NH4]+ for C32H29NO2Cl: 494.1881, found: 494.1892.

3-(2,4-Diphenylnaphthalen-1-yl)-1-(furan-2-yl)propan-1-one (3ai):



GP was carried out with o-(alkyne)styrene 1a (84 mg, 0.3 mmol), alcohol 2i (112 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere. Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 94:6) furnished the naphthalene ketone 3ai (75 mg, 62%) as a pale yellow viscous liquid. TLC (petroleum ether/ethyl acetate 90:10): Rf(1a) = 0.7, Rf(3ai) = 0.4, UV detection. IR (MIR-ATR, 4000–600 cm-1): max = 3057, 2929, 1671, 1465, 761, 701 cm-1. 1H NMR (400 MHz, CDCl3): δ = 8.20 (d, J = 8.6 Hz, 1H, Ar–H), 7.99 (d, J = 8.5 Hz, 1H, Ar–H), 7.58 (t, J = 7.6 Hz, 1H, Ar–H), 7.54–7.35 (m, 12H, Ar–H), 7.34 (s, 1H, Ar–H), 6.92 (d, J = 3.5 Hz, 1H, Ar–H), 6.45 (dd, J = 3.5, 1.7 Hz, 1H, Ar–H), 3.55– 3.45 (m, 2H, CH2), 3.17–3.08 (m, 2H, CH2) ppm. 13C{1H} NMR (100 MHz, CDCl3): δ = 188.3 (C=O), 152.3 (Ar–C), 146.3 (Ar– CH), 142.2 (Ar–C), 140.5 (Ar–C), 139.2 (Ar–C), 138.7 (Ar–C), 133.2 (Ar–C), 132.0 (Ar–C), 131.4 (Ar–C), 130.1 (2 × Ar–CH), 129.4 (Ar–CH), 129.3 (2 × Ar–CH), 128.3 (2 × Ar–CH), 128.2 (2 × Ar–CH), 127.2 (Ar–CH), 127.1 (Ar–CH), 127.0 (Ar–CH), 126.5 (Ar–CH), 125.6 (Ar–CH), 124.3 (Ar–CH), 117.1 (Ar–CH), 112.1 (Ar–CH), 39.9 (CH2), 24.0 (CH2) ppm. HRMS (ESI) calculated [M+H]+ for C29H23O2: 403.1693, found: 403.1697.

3-(2,4-Diphenylnaphthalen-1-yl)-1-(thiophen-2-yl)propan-1-one (3aj): GP was carried out with o-(alkyne)styrene 1a (84 mg, 0.3 mmol), alcohol 2j (126 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere. Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 95:5) furnished the naphthalene ketone 3aj (80 mg, 64%) as a pale yellow viscous liquid. TLC (petroleum ether/ethyl acetate 90:10): Rf(1a) = 0.7, Rf(3aj) = 0.5, UV detection. IR (MIR-ATR, 4000–600 cm-1): max = 3057, 2929, 1657, 1411, 1267, 728, 700 cm-1.


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1


7.62–7.55 (m, 2H, Ar–H), 7.54–7.37 (m, 11H, Ar–H), 7.34 (s, 1H, Ar–H), 7.32 (dd, J = 3.8, 1.1 Hz, 1H, Ar–H), 7.01 (dd, J = 4.9, 3.8 Hz, 1H, Ar–H), 3.58–3.49 (m, 2H, CH2), 3.22–3.14 (m, 2H, CH2) ppm. 13C{1H} NMR (100 MHz, CDCl3): δ = 192.2 (C=O), 143.9 (Ar–C), 142.2 (Ar– C), 140.5 (Ar–C), 139.2 (Ar–C), 138.7 (Ar–C), 133.6 (Ar–CH), 133.2 (Ar–C), 132.0 (Ar–C), 131.9 (Ar–CH), 131.4 (Ar–C), 130.2 (2 × Ar–CH), 129.4 (Ar–CH), 129.3 (2 × Ar–CH), 128.4 (2 × Ar–CH), 128.3 (2 × Ar–CH), 128.0 (Ar–CH), 127.3 (Ar–CH), 127.2 (Ar–CH), 127.0 (Ar–CH), 126.6 (Ar–CH), 125.7 (Ar–CH), 124.3 (Ar–CH), 40.6 (CH2), 24.5 (CH2) ppm. HRMS (ESI) calculated [M+H]+ for C29H23OS: 419.1464, found: 419.1463.

1-(4-(3-Methoxyphenyl)-2-phenylnaphthalen-1-yl)octan-3-one (3nk): GP was carried out with o-(alkyne)styrene 1n (93 mg, 0.3 mmol), alcohol 2k (115 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere. Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 96:4) furnished the naphthalene ketone 3nk (86 mg, 66%) as a light yellow viscous liquid. TLC (petroleum ether/ethyl acetate 90:10): Rf(1n) = 0.7, Rf(3nk) = 0.6, UV detection. IR (MIR-ATR, 4000–600 cm-1): max = 2931, 2863, 1711, 1589, 1458, 1323, 1045, 766, 702 cm-1. 1H NMR (400 MHz, CDCl3): δ = 8.09 (d, J = 8.5 Hz, 1H, Ar–H), 8.01 (d, J = 8.4 Hz, 1H, Ar–H), 7.60–7.53 (m, 1H, Ar–H), 7.47–7.40 (m, 3H, Ar–H), 7.39–7.34 (m, 4H, Ar–H), 7.33 (s, 1H, Ar–H), 7.08 (d, J = 7.5 Hz, 1H, Ar–H), 7.06–7.04 (m, 1H, Ar–H), 6.95 (dd, J = 8.2, 2.6 Hz, 1H, Ar–H), 3.82 (s, 3H, OCH3), 3.40–3.29 (m, 2H, CH2), 2.76–2.66 (m, 2H, CH2), 2.28 (t, J = 7.5 Hz, 2H, CH2), 1.56–1.46 (m, 2H, CH2), 1.33–1.17 (m, 4H, 2 × CH2), 0.87 (t, J = 7.1 Hz, 3H, CH3) ppm.

C{1H} NMR (100 MHz, CDCl3): δ = 210.3 (C=O), 159.4 (Ar–C), 142.1

13



(Ar–C), 141.8 (Ar–C), 139.0 (Ar–C), 138.3 (Ar–C), 133.6 (Ar–C), 131.8 (Ar–C), 131.3 (Ar–C), 129.1 (4 × Ar–CH), 128.2 (2 × Ar–CH), 127.1 (Ar–CH), 127.0 (Ar–CH), 126.4 (Ar–CH), 125.6 (Ar–CH), 124.2 (Ar–CH), 122.6 (Ar–CH), 115.6 (Ar–CH), 112.8 (Ar–CH), 55.2 (OCH3), 43.7 (CH2), 42.6 (CH2), 31.3 (CH2), 23.6 (CH2), 23.3 (CH2), 22.4 (CH2), 13.9 (CH3) ppm. HRMS (ESI) calculated [M+H]+ for C31H33O2: 437.2475, found: 437.2476.

3-(2-(2-Chlorophenyl)-4-phenylnaphthalen-1-yl)-1-cyclohexylpropan-1-one (3fl): GP was carried out with o-(alkyne)styrene 1f (94 mg, 0.3 mmol), alcohol 2l (126 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere. Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 95:5) furnished the naphthalene ketone 3fl (81 mg, 60%) as a pale yellow viscous liquid. TLC (petroleum ether/ethyl acetate 90:10): Rf(1f) = 0.6, Rf(3fl) = 0.5, UV detection. IR (MIR-ATR, 4000–600 cm-1): max = 2927, 2853, 1702, 1442, 1263, 733, 698 cm-1. 1


7.60–7.54 (m, 1H, Ar–H), 7.53–7.44 (m, 6H, Ar–H), 7.43–7.37 (m, 1H, Ar–H), 7.35–7.31 (m, 3H, Ar–H), 7.23 (s, 1H, Ar–H), 3.24–3.09 (m, 2H, CH2), 2.81–2.62 (m, 2H, CH2), 2.23–2.13 (m, 1H, CH), 1.74–1.67 (m, 4H, 2 × CH2), 1.65–1.60 (m, 1H, CH), 1.26–1.13 (m, 5H, 2 × CH2, CH) ppm.

13


(Ar–C), 136.1 (Ar–C), 134.5 (Ar–C), 133.4 (Ar–C), 131.9 (Ar–C), 131.6 (Ar–C), 131.2 (Ar– CH), 130.2 (2 × Ar–CH), 129.6 (Ar–CH), 128.9 (Ar–CH), 128.7 (Ar–CH), 128.2 (2 × Ar–CH), 127.2 (Ar–CH), 127.0 (Ar–CH), 126.6 (Ar–CH), 126.4 (Ar–CH), 125.8 (Ar–CH), 124.3 (Ar– CH), 50.7 (CH), 40.9 (CH2), 28.3 (2 × CH2), 25.8 (CH2), 25.6 (2 × CH2), 23.7 (CH2) ppm. HRMS (ESI) calculated [M+H]+ for C31H30OCl: 453.1980, found: 453.1979.


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3-(2,4-Diphenylnaphthalen-1-yl)-1-(4-hydroxyphenyl)propan-1-one (3am): GP was carried out with o-(alkyne)styrene 1a (84 mg, 0.3 mmol), alcohol 2m (135 mg, 0.9 mmol) and, PdCl2 (5 mg, 0.03 mmol) in 1,4-dioxane (1 mL) at 60 °C for 24 h under open atmosphere. Purification of the crude mixture by silica gel column chromatography (petroleum ether/ethyl acetate, 100:0 to 90:10) furnished the naphthalene ketone 3am (89 mg, 69%) as a pale yellow viscous liquid. TLC (petroleum ether/ethyl acetate 90:10): Rf(1a) = 0.7, Rf(3am) = 0.2, UV detection. IR (MIR-ATR, 4000–600 cm-1): max = 3206, 2979, 1646, 1586, 1439, 1281, 702 cm-1. 1H NMR (400 MHz, CDCl3) δ 8.19 (d, J = 8.5 Hz, 1H, Ar–H), 8.03–7.96 (m, 1H, Ar– H), 7.73–7.63 (m, 2H, Ar–H), 7.59–7.37 (m, 12H, Ar–H), 7.34 (s, 1H, Ar–H), 6.85–6.75 (m, 2H, Ar–H), 6.20 (brs, 1H, OH), 3.57–3.44 (m, 2H, CH2), 3.23–3.12 (m, 2H, CH2) ppm.

13

C{1H}

NMR (100 MHz, CDCl3): δ = 198.5 (C=O), 160.2 (Ar–C), 142.3 (Ar–C), 140.5 (Ar–C), 139.2 (Ar–C), 138.6 (Ar–C), 133.5 (Ar–C), 132.0 (Ar–C), 131.4 (Ar–C), 130.8 (2 × Ar–CH), 130.2 (2 × Ar–CH), 129.5 (Ar–C), 129.34 (Ar–CH), 129.30 (2 × Ar–CH), 128.4 (2 × Ar–CH), 128.2 (2 × Ar–CH), 127.3 (Ar–CH), 127.1 (Ar–CH), 127.0 (Ar–CH), 126.6 (Ar–CH), 125.7 (Ar–CH), 124.3 (Ar–CH), 115.3 (2 × Ar–CH), 39.8 (CH2), 24.6 (CH2) ppm. HRMS (ESI) calculated [M+H]+ for C31H25O2: 429.1849, found: 429.1848.

ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI: 1

H NMR and 13C NMR spectra for all starting materials and products.

X-ray data for compound 3ae (CIF)



AUTHOR INFORMATION Corresponding Author * E-mail: [email protected]

ORCID Gedu Satyanarayana: 0000-0002-6410-5421

Author Contributions The manuscript was written through the contributions of all authors. / All authors have given approval to the final version of the manuscript. Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT We greatly acknowledge the financial support from DST-SERB (Department of Science and Technology, Science and Engineering Research Board, Grant No. EMR/2017/005312), New Delhi. P. R. thanks DST-SERB for the award of National Postdoctoral Fellowship (Diary No. SERB/F/7226/2017-2018). REFERENCES


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Palladium-Catalyzed Aerobic Oxidative Coupling of ortho-(Alkynyl

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