Palladium-Catalyzed Catellani-Type bis-Silylation and bis

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Palladium-Catalyzed Catellani-Type bis-Silylation and bis-Germanylation of Aryl Iodides and Norbornenes Weiwei Lv, Jia Yu, Bailu Ge, Si Wen, and Guolin Cheng J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b02018 • Publication Date (Web): 21 Sep 2018 Downloaded from http://pubs.acs.org on September 21, 2018

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The Journal of Organic Chemistry

Palladium-Catalyzed Catellani-Type bis-Silylation and bisGermanylation of Aryl Iodides and Norbornenes Weiwei Lv, Jia Yu, Bailu Ge, Si Wen, and Guolin Cheng* College of Materials Science & Engineering, Huaqiao University, Xiamen 361021, China

ABSTRACT: A palladium-catalyzed three-component reaction of aryl iodides, norbornenes, and hexamethyldisilane/hexamethyldigermane has been developed for the assembly of highly functionalized disilanes/digermanes. The potential synthetic utility of this methodology was highlighted by the late-stage manipulations of natural products and the iterative C–H bissilylation for the synthesis of highly decorated arenes.

INTRODUCTION Organosilanes play an important role in organic chemistry,1 materials science,2 and pharmaceutical industry.3 Thus, it continues to be an area of intense interest to develop practical and efficient methods for the synthesis of organosilanes. Current methods for the preparation of organosilanes include olefin/alkyne hydrosilylation4 and the cross-coupling of a silicon electrophile with an organic nucleophile.5 However, these methods usually require pre-functionalized precursors. In addition, the installation a silyl group at secondary carbon center in a regio-, and stereoselective manner has been a longstanding challenge.6 The Pd/norbornene (NBE)-based Catellani-type ortho- and ipso- dual functionalization reaction of aryl halides leading to highly substituted arenes is of great significance in organic syntheses. This elegant reaction was well developed by several groups, including Catellani,7 Lautens,8 Yu,9 Bach,10 Dong,11 Gu,12 and others.13 The ortho- arylation, alkylation, amination, alkynylation, chlorination, as well as acylation were achieved via this approach in the past decades.14 A range of nucleophiles or olefins were used as terminal reagents (Scheme 1a).11a In addition, NBEs could serve as terminal reagents yielding complex skeletons containing the norbornane moiety (Scheme 1b).15 Our group recently disclosed an Pd-catalyzed Catellani-type silylation reaction using oxanorbornadiene as an ortho-C−H activator and ethylene surrogate for the assembling of (Z)-β-substituted vinylsilanes.16 As research continues, we report herein a palladium-catalyzed Catellani-type bissilylation reaction of aryl iodides and NBEs, affording disilanes bearing one C(sp2)–Si bond and one secondary C(sp3)– Si bond stereoselectively (Scheme 1c).17–19

Scheme 1. Catellani-Type Ipso- and Ortho- Dual Functionalizations of Aryl Halides.

RESULTS AND DISCUSSION Initially, we began the studies with 1-iodonaphthalene 1a, hexamethyldisilane 2a, and NBE 3a to explore the reaction conditions. After systematic screening of the reaction conditions, the optimal conditions were achieved to be: Pd(OAc)2 (10 mol %), PPh3 (20 mol %), and Cs2CO3 (2.0 equiv) in DMF under N2 at 60 oC to yield the desired disilylated product 4a in 88% NMR yield (Table 1, entry 1). Under other conditions, no

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product or only low yields were observed (see SI for details). In the absence of either the Pd catalyst or the base, no desired product 4a was formed (entries 2, 3). Replacing Cs2CO3 with K2CO3 decreased the yield to 56% (entry 4). The use of tri(2furyl)phosphane (TFP) in place of PPh3 afforded a similar result (entry 5). Only trace of 4a was observed without ligand (entry 6). A remarkable solvent effect was observed using less polar solvents, which inhibited the reaction completely (entries 7, 8). Table 1. Role of Select Parametersa

entry

deviation from standard conditions

yield (%)b

1

none

88

2

no Pd(OAc)2

0

3

no Cs2CO3

0

4

K2CO3 instead of Cs2CO3

56

5

TFP instead of PPh3

87

6

no PPh3

trace

7

1,2-dichloroethane instead of DMF

0

8

toluene instead of DMF

0

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tolerates various functional groups, such as halogen, ester, Weinreb amide, trifluoromethoxy, acetamide, as well as hydroxyl. However, the use of coordinative thiophene substrate does lead to a slight decrease yield of the disilane 5r. Finally, phenylalanine- and estrone-containing products 5s, 5t were also synthesized in 51% and 54% yields, respectively. It should be noted that exclusive exo-isomers were formed in all cases of the aforementioned bis-silylation reactions, as indicated by the X-ray structures of 4l and 5i. Scheme 2. Scope of NBEsa

a

Reaction conditions: 1a (0.1 mmol), 2a (0.15 mmol), 3a (0.2 mmol), Pd(OAc)2 (10 mol%), PPh3 (20 mol%), and Cs2CO3 (0.2 mmol) in DMF (1 mL) under nitrogen atmosphere for 12 h. bDetermined by 1H NMR analysis of the crude products using CH2Br2 as an internal standard. DMF = N,N-dimethylformamide.

With the optimal conditions in hand, the three-component reaction was extended to norbornene derivatives by using 1iodonaphthalene 1a and hexamethyldisilane 2a as partners (Scheme 2). The silylation of alkenes 3a−n afforded the expected disilylated products 4a−n in moderate to excellent yields. A variety of valuable functional groups was tolerated, including ester, benzyl, cyano, trifluoromethyl, and vinyl. For substrates bearing a vinylic substituent, the reactions occurred exclusively at the most strained double bond to yield the desired products 4g and 4h in 83% and 59% yields, respectively. Norbornadiene (NBD) also participated in the reaction and gave the corresponding product 4i in 70% yield, with retention of a double bond in the bicyclic ring. More importantly, the tetrasilylated products 4i′ and 4i′′ were obtained in 87% combined yield, however, reduced amounts of NBD is necessary. Notably, 7-oxanorbornene 3j, 7-oxanorbornadiene 3k ， as well as 7-oxabenzonorbornadiene 3l were suitable substrates for this domino reaction without the ring-opening to give the disilylated products 4j−l in high yields. Finally, 7azabenzonorbornadienes could also be used in this transformation with extremely high efficiency 4m, 4n. After demonstrating the scope of NBEs, we next examined the scope of the aryl iodides (Scheme 3). Thus, a variety of aryl iodides (1) were smoothly converted into the corresponding products 5a−t in 45–92% yields. Aryl iodides not bearing ortho- substituents reacted with 3l and hexamethyldisilane to give the desired products 5i−t, however, as expected on the basis of previous report,15c yields are not as good as those for aryl iodides bearing ortho-substituents 5a−h. The reaction

a Reaction conditions: 1a (0.1 mmol), 2a (0.15 mmol), 3 (0.2 mmol), Pd(OAc)2 (10 mol%), PPh3 (20 mol%), and Cs2CO3 (0.2 mmol) in DMF (1 mL) at 60 oC under nitrogen atmosphere for 12 h. b4 equiv of NBE were used. c1a (0.3 mmol), 2a (0.3 mmol), and NBD (0.1 mmol) were used, yield based on NBD. d1bromonaphthalene was used as substrate.

Encouraged by the successful bis-silylation reaction, we proceed to explore this strategy for the bis-germanylation reaction. We envisioned that digermanes might also be generated by using hexamethyldigermane instead of hexamethyldisilane under the standard reaction conditions (Scheme 4). To our delight, for a series of NBEs and aryl iodides, the palladiumcatalyzed three-component reaction afforded the corresponding digermanes 6a−j in moderate to excellent yields. The scalability of this method was demonstrated by the bissilylation reaction of 1a (5 mmol) with 2a and 3l. This reaction completed within 24 h, producing 1.88 g of the desired product 4l in 90% yield (Scheme 5a). It is worth mentioning that the selective transformation of aryl TMS group to aryl iodides 7a, 7b was achieved with retention the alkyl TMS group (Scheme 5b). Then, we performed an iterative bissilylation using the newly synthesized aryl iodide 7b as the starting material, and the trisilylated product 8 was obtained in 62% yield. Furthermore, we found that the aryl iodide 7b could successfully undergo deoxyaromatization reaction in acidic conditions, providing 2-iodo-1,2'-binaphthalene 9 in almost quantitative yield.


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Scheme 3. Scope of Aryl Iodidesa

When an extra 1.5 equiv of terminal reagents (methyl acrylate, phenylboronic acid, and isopropanol) was added, 4a was formed exclusively (83−87% yields), and no corresponding coupling products 10a and 10b or reductive product 10c could be detected (Scheme 6). Scheme 6. Control Experiments

a

Reaction conditions: 1 (0.1 mmol), 2a (0.15 mmol), 3l (0.2 mmol), Pd(OAc)2 (10 mol%), PPh3 (20 mol%), and Cs2CO3 (0.2 mmol) in DMF (1 mL) at 100 oC under nitrogen atmosphere for 12 h. Scheme 4. Scope of NBEs and Aryl Iodidesa On the basis of these results and literature reports, we proposed that the reaction would proceed as shown in the introduction (Scheme 7). Initially, the palladacycle III is formed via Ar−I oxidative addition to Pd0 and subsequent NBEmediated vicinal C−H activation. Then oxidative addition of hexamethyldisilane to palladacycle III generating a palladacycle V.17b Finally, palladacycle V undergoes Scheme 7. Plausible Catalytic Cycle.

a

Reaction conditions: 1 (0.1 mmol), 2b (0.15 mmol), 3 (0.2 mmol), Pd(OAc)2 (10 mol%), PPh3 (20 mol%), and Cs2CO3 (0.2 mmol) in DMF (1 mL) at 100 oC under nitrogen atmosphere for 12 h. bReaction was carried out at 60 oC. Scheme 5. Gram-Scale Reaction and Derivatization Reactions



reductive elimination to give intermediate VI, which could further undergo a second reductive elimination to giving the desired product 4 and regenerate the Pd0 catalyst. Alternatively, the metathesis pathway involving intermediate IV cannot be precluded.

CONCLUSION In conclusion, we have developed a palladium-catalyzed Catellani-type bis-silylation and bis-germanylation of aryl iodides and norbornenes. This methodology provides a practical and stereoselective approach for the synthesis of disilane and digermane products with high efficiency. This approach is compatible with a wide spectrum of readily available functionalized aryl iodides and NBEs.

EXPERIMENTAL SECTION General Information. All the solvents were used without further purification. The other commercial chemicals were used without further purification. All reactions were performed under an inert atmosphere of nitrogen in flame-dried glassware, unless otherwise stated. Analytical thin layer chromatography was performed on 0.25 mm silica gel 60-F254. Visualization was carried out with UV light and Vogel’s permanganate. Preparative TLC was performed on 1.0 mm silica gel. 1H NMR spectra were recorded on Bruker DRX-500 instrument (500 MHz). 13C NMR spectra were recorded on Bruker DRX-500 instrument (126 MHz) and Bruker DRX-400 instrument (100 MHz) were fully decoupled by broad band proton decoupling. High-resolution mass spectra (HRMS) were recorded on an Agilent 1290 Mass spectrometer using ESI-TOF (electrospray ionization-time of flight). NMR spectra were recorded in CDCl3. 1H NMR spectra were referenced to residual CHCl3 at 7.26 ppm, and 13C NMR spectra were referenced to the central peak of CDCl3 at 77.0 ppm. Chemical shifts (δ) are reported in ppm, and coupling constants (J) are in Hertz (Hz). Multiplicities are reported using the following abbreviations: s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet. Procedure for Preparation of 3d. Triethylamine (1.5 mL) was added to a solution of cis-5-norbornene-endo-2,3dicarboxylic anhydride (820 mg, 5 mmol) and aminoacetonitrile hydrochloride (463 mg, 5 mmol) in Chloroform (10 mL). The solution was stirred for 12 h at 60 ℃. After the reaction finished, then the cooled reaction mixture was washed with 2 M hydrochloric acid (3 × 5 mL) and the aqueous phase backextracted with 30 mL ethyl acetate. The combined organic phase was washed with saturated ammonium carbonate (2 × 10 mL) and 10 ml H2O, dried over sodium sulfate, filtered and concentrated. The residue was purified by column chromatography (ethyl acetate : petroleum ether = 1:1) to yield the desired N-(cyanomethyl)-cis-5-norbornene-endo-2,3dicarboximide as white solid (889 mg, 88% yied), mp 161162 ℃. 1H NMR (500 MHz, CDCl3) δ 6.17 (t, J = 1.8 Hz, 2H), 4.20 (s, 2H), 3.46 (dt, J = 4.7, 1.7 Hz, 2H), 3.37 (dd, J = 2.9, 1.5 Hz, 2H), 1.78 (dt, J = 8.9, 1.7 Hz, 1H), 1.58 (d, J = 8.9 Hz, 1H); 13C NMR (126 MHz, CDCl3) δ 175.4, 134.6, 113.1, 52.2, 46.0, 45.3, 25.1; HRMS (ESI-TOF) m/z: calcd for C11H11N2O2+: 203.0815 (M + H)+, found: 203.0812. Procedure for the Preparation of 3e. Triethylamine (1.85 mL) was added to a solution of cis-5-norbornene-endo-2,3dicarboxylic anhydride (820 mg, 5 mmol) and glycine methyl ester hydrochloride (753 mg, 6 mmol) in toluene (20.0 mL).

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The resulting mixture was heated at 120 ℃ for 15 h. then the cooled reaction mixture was washed with 2 M hydrochloric acid (3 × 5 mL) and the aqueous phase back-extracted with 30 mL ethyl acetate. The combined organic phase was washed with saturated ammonium carbonate (2 × 10 mL) and 10 mL H2O, dried over sodium sulfate, filtered and concentrated. The residue was purified by column chromatography (ethyl acetate : petroleum ether = 1:1) to colorless oil. The colorless oil slowly crystallized and recrystallized from ethyl acetate and was obtained the desired methyl 2-1,3-dioxo-1,3,3a,4,7,7ahexahydro-2H-4,7-methanoisoindol-2-yl)acetate as white solid in an overall yield of 72% (846 mg), mp 96-97 ℃. 1H NMR (500 MHz, CDCl3) δ 6.14 (t, J = 1.7 Hz, 2H), 4.09 (s, 2H), 3.72 (s, 3H), 3.42 (dt, J = 4.6, 1.6 Hz, 2H), 3.36 (dd, J = 2.9, 1.5 Hz, 2H), 1.76 (dt, J = 8.8, 1.6 Hz, 1H), 1.57 (d, J = 9.7 Hz, 1H);13C NMR (126 MHz, CDCl3) δ 176.7, 167.0, 134.5, 52.4, 52.2, 46.1, 44.9, 39.0; HRMS (ESI-TOF) m/z: calcd for C12H13NNaO4+: 258.0737 (M + Na)+, found: 25.8.0736 Procedure for the Preparation of 3f. Triethylamine (1.5 ml, 10 mmol) was added to a solution of cis-5-norbornene-endo2,3-dicarboxylic anhydride (820 mg, 5mmol) and 2,2,2trifluoroethylamine hydrochloride (678 mg, 5 mmol) in toluene (10.0 mL). The resulting mixture was heated at 120 ℃ for 15 h. then the cooled reaction mixture was washed with 2 M hydrochloric acid (3 × 5 mL) and the aqueous phase backextracted with 30 mL ethyl acetate. The combined organic phase was washed with saturated ammonium carbonate (2 × 10 mL) and 10 mL H2O, dried over sodium sulfate, filtered and concentrated. The residue was purified by column chromatography (ethyl acetate : petroleum ether = 1:1) to yield the desired N-trifluoroethyl-cis-5-norbornene-endo-2,3dicarboximide as white solid (588 mg, 48% yiled), mp 118119 ℃. 1H NMR (500 MHz, CDCl3) δ 6.12 (t, J = 1.7 Hz, 2H), 3.98 (q, J = 8.7 Hz, 2H), 3.45 (dt, J = 4.6, 1.7 Hz, 2H), 3.35 (dd, J = 2.9, 1.5 Hz, 2H), 1.76 (dt, J = 8.9, 1.6 Hz, 1H), 1.56 (d, J = 8.9 Hz, 1H);13C NMR (126 MHz, CDCl3) δ 176.0, 134.4, 123.0 (q, J = 280.3 Hz), 52.1, 45.8, 45.3, 38.9 (q, J = 36.3 Hz); HRMS (ESI-TOF) m/z: calcd for C11H11F3NO2+: 246.0736 (M + H)+, found: 246.0734. Procedure for the Preparation of 3h. A solution of Nallylamine (0.285 g, 5 mmol) and cis-5-Norbornene-exo-2,3dicarboxylic anhydride (1.4774 g, 9 mmol) in glacial AcOH was heated at 120℃ for 15 h. then the reaction mixture was cooled to room temperature ,The AcOH was removed under reduced pressure, the organic layer was separated, and the aqueous phase was extracted with CH2Cl2 (3 × 10 ml). The organic phase was washed with H2O(3× 20 ml). The combined organic extracts were dried sodium sulfate, filtered , and concentrated in vacuo. The residue was purified by column chromatography (ethyl acetate : petroleum ether = 1:1) to yield the desired N-allyl-cis-5-norbornene-exo-2,3dicarboximide as a colorless oil (0.9034 g, 89% yiled). 1H NMR (500 MHz, CDCl3) δ 6.30 (t, J = 1.8 Hz, 2H), 5.82 – 5.74 (m, 1H), 5.27 (dd, J = 17.1, 1.3 Hz, 1H), 5.20 (dd, J = 10.2, 1.1 Hz, 1H), 4.08 (d, J = 6.2 Hz, 2H), 3.31 – 3.27 (m, 2H), 2.71 (d, J = 1.2 Hz, 2H), 1.54 – 1.49 (m, 1H), 1.25 (d, J = 9.8 Hz, 1H); 13C NMR (126 MHz, CDCl3) δ 177.5, 137.8, 130.6, 118.9, 47.7, 45.1, 42.6, 40.8; HRMS (ESI-TOF) m/z: calcd for C12H13NNaO2+: 226.0838 (M + Na)+, found: 226.0838. Procedure for the Preparation of 4. A dried 10 mL Schlenk tube was charged with 1-iodonaphthalene 1a (25.4 mg, 0.1


Page 5 of 13 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


mmol, 1 equiv), hexamethyldisilane 2a (22 mg, 0.15 mmol), Pd(OAc)2 (2.3 mg, 0.01 mmol, 10 mol %), triphenylphosphine (PPh3) (5.3 mg, 0.02 mmol, 20 mol %), norbornene 3a (19 mg, 0.2 mmol, 2 equiv), Cs2CO3 (66 mg, 0.2 mmol, 2 equiv), and DMF (1 mL) and then the tube was evacuated and back filled with nitrogen (10 times). The reaction mixture was heated to 60 °C for 12 hours under vigorous stirring. Upon completion, the reaction mixture was cooled to room temperature, diluted with ethyl acetate, and filtered through a pad of celite. The filtrate was concentrated under vacuum, and the resulting residue was purified by preparative thin layer chromatography (PTLC) with hexane to give the corresponding products trimethyl(1-(3-(Trimethylsilyl)bicyclo[2.2.1]heptan-2yl)naphthalen-2-yl)silane (4a) (32.3 mg, 88%) as a colorless oil. Then the colorless oil slowly crystallized as a white solid. mp 63-64 ℃. 1H NMR (500 MHz, CDCl3) δ 8.63 – 8.60 (m, 1H), 7.81 – 7.77 (m, 1H), 7.67 (d, J = 8.3 Hz, 1H), 7.57 – 7.54 (m, 1H), 7.45 – 7.39 (m, 2H), 3.81 (d, J = 10.9 Hz, 1H), 3.07 (s, 1H), 2.45 (d, J = 4.2 Hz, 1H), 2.33 (d, J = 9.6 Hz, 1H), 1.95 – 1.89 (m, 1H), 1.73 – 1.66 (m, 1H), 1.64 – 1.52 (m, 3H), 1.49 – 1.43 (m, 2H), 0.42 (s, 9H), -0.72 (s, 9H); 13C NMR (126 MHz,) δ 148.4, 139.0, 135.3, 132.1, 131.4, 128.6, 126.7, 126.1, 125.5, 124.4, 54.2, 45.6, 42.7, 40.4, 39.3, 34.0, 32.2, 2.1, -1.0; HRMS (ESI-TOF) m/z: calcd for C23H34NaSi2+: 389.2091 (M + Na)+, found: 389.2093. Dimethyl-5-(trimethylsilyl)-6-(2-(trimethylsilyl)naphthalen1-yl)bicyclo[2.2.1]heptane-2,3-dicarboxylate (4b) (28.7 mg, 60%) was prepared from typical procedure (ethyl acetate : hexane = 1 : 20) as white solid. mp 140-141 ℃. δ 8.63 – 8.59 (m, 1H), 7.81 – 7.77 (m, 1H), 7.69 – 7.63 (m, 2H), 7.43 – 7.37 (m, 2H), 4.34 (d, J = 10.8 Hz, 1H), 3.72 (s, 3H), 3.68 (s, 3H), 3.34 (dd, J = 11.8, 4.6 Hz, 1H), 3.15 (dd, J = 11.8, 3.5 Hz, 1H), 2.72 – 2.69 (m, 1H), 2.59 (d, J = 10.2 Hz, 1H), 2.06 – 2.03 (m, 1H), 1.80 (d, J = 10.1 Hz, 1H), 1.61 (s, 1H), 0.45 (s, 9H), 0.74 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 172.8, 172.0, 146.7, 140.5, 135.5, 132.0, 132.0, 129.1, 126.5, 126.0, 125.1, 124.6, 51.6, 51.5, 49.6, 47.63, 47.62, 46.5, 43.9, 42.3, 37.7, 2.0, -1.0; HRMS (ESI-TOF) m/z: calcd for C27H39O4Si2+: 483.2381 (M + H)+, found: 483.2379. 2-Benzyl-5-(trimethylsilyl)-6-(2-(trimethylsilyl)naphthalen1-yl)hexahydro-1H-4,7-methanoisoindole-1,3(2H)-dione (4c) (47.0 mg, 89%) was prepared from typical procedure (ethyl acetate : hexane = 1 : 4) as white solid. mp 230-231 ℃. 1H NMR (500 MHz, CDCl3) δ 8.55 (d, J = 8.5 Hz, 1H), 7.85 – 7.81 (m, 1H), 7.72 (d, J = 8.3 Hz, 1H), 7.62 (d, J = 8.3 Hz, 1H), 7.50 – 7.41 (m, 4H), 7.38 – 7.30 (m, 3H), 4.75 (s, 2H), 3.98 (s, 1H), 3.75 (d, J = 10.8 Hz, 1H), 3.40 – 3.31 (m, 2H), 2.87 – 2.82 (m, 1H), 2.80 (d, J = 10.5 Hz, 1H), 2.02 (d, J = 10.3 Hz, 1H), 1.73 (dd, J = 10.9, 2.1 Hz, 1H), 0.45 – 0.41 (m, 9H), -0.69 – -0.74 (m, 9H); 13C NMR (126 MHz, CDCl3) δ 177.5, 176.9, 145.3, 139.7, 135.9, 135.6, 131.7, 131.6, 129.1, 129.1, 128.6, 128.0, 127.0, 125.5, 125.4, 124.9, 51.5, 50.9, 50.2, 45.8, 45.1, 42.7, 41.3, 38.8, 2.0, -1.2; HRMS (ESI-TOF) m/z: calcd for C32H39NNaO2Si2+: 548.2412 (M + Na)+, found : 548.2412. 2-(1,3-Dioxo-5-(trimethylsilyl)-6-(2(trimethylsilyl)naphthalen-1-yl)octahydro-2H-4,7methanoisoindol-2-yl)acetonitrile (4d) (23.3 mg, 49%) was prepared from typical procedure (ethyl acetate : hexane = 1 : 1) as white solid. mp 236-237 ℃. 1H NMR (500 MHz, CDCl3) δ 8.47 (d, J = 8.4 Hz, 1H), 7.83 – 7.79 (m, 1H), 7.69 (d, J = 8.3 Hz, 1H), 7.55 (d, J = 8.3 Hz, 1H), 7.46 – 7.39 (m, 2H), 4.46 –

4.37 (m, 2H), 3.99 (d, J = 3.6 Hz, 1H), 3.60 (d, J = 10.8 Hz, 1H), 3.54 – 3.47 (m, 2H), 2.88 – 2.84 (m, 1H), 2.80 (d, J = 10.5 Hz, 1H), 2.05 (d, J = 10.3 Hz, 1H), 1.56 (dd, J = 10.8, 2.1 Hz, 1H), 0.29 (s, 9H), -0.76 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 175., 175.2, 144.8, 139.3, 135.6, 131.6, 131.5, 129.3, 127.3, 125.6, 125.3, 125.1, 113.1, 51.7, 51.0, 50.2, 46.0, 45.2, 41.5, 39.0, 25.9, 2.0, -1.2; HRMS (ESI-TOF) m/z: calcd for C27H34N2NaO2Si2+: 497.2051 (M + Na)+,found: 497.2050. Methyl 2-(1,3-dioxo-5-(trimethylsilyl)-6-(2(trimethylsilyl)naphthalen-1-yl)octahydro-2H-4,7methanoisoindol-2-yl)acetate (4e) (43.7 mg, 86%) was prepared from typical procedure (ethyl acetate : hexane = 1 : 1) as white solid. mp 234-235 ℃. 1H NMR (500 MHz, CDCl3) δ 8.51 (d, J = 8.9 Hz, 1H), 7.82 – 7.77 (m, 1H), 7.68 (d, J = 8.3 Hz, 1H), 7.56 (d, J = 8.3 Hz, 1H), 7.45 – 7.39 (m, 2H), 4.36 – 4.27 (m, 2H), 3.96 (d, J = 4.3 Hz, 1H), 3.77 (s, 3H), 3.65 (d, J = 10.8 Hz, 1H), 3.54 – 3.46 (m, 2H), 2.84 (d, J = 4.5 Hz, 1H), 2.78 (d, J = 10.5 Hz, 1H), 2.05 (d, J = 10.3 Hz, 1H), 1.62 (dd, J = 10.9, 2.1 Hz, 1H), 0.31 (s, 9H), -0.76 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 176.9, 176.5, 167.0, 145.2, 139.5, 135.5, 131.7, 131.5, 129.2, 127.1, 125.5, 125.4, 124.9, 52.7, 51.7, 51.0, 50.1, 45.9, 45.2, 41.4, 39.6, 38.9, 1.9, -1.2; HRMS (ESITOF) m/z: calcd for C28H37NNaO4Si2+: 530.2153 (M + Na)+,found: 530.2153. 2-(2,2,2-Trifluoroethyl)-5-(trimethylsilyl)-6-(2(trimethylsilyl)naphthalen-1-yl)hexahydro-1H-4,7methanoisoindole-1,3(2H)-dione (4f) (45.6 mg, 88%) was prepared from typical procedure (ethyl acetate : hexane = 1 : 1) as white solid. mp 247-248 ℃. 1H NMR (500 MHz, CDCl3) δ 8.52 (d, J = 8.5 Hz, 1H), 7.85 – 7.80 (m, 1H), 7.72 (d, J = 8.3 Hz, 1H), 7.59 (d, J = 8.3 Hz, 1H), 7.48 – 7.41 (m, 2H), 4.27 – 4.16 (m, 2H), 4.01 (d, J = 3.2 Hz, 1H), 3.64 (d, J = 10.9 Hz, 1H), 3.58 – 3.51 (m, 2H), 2.90 – 2.85 (m, 1H), 2.82 (d, J = 10.5 Hz, 1H), 2.10 – 2.06 (m, 1H), 1.64 (dd, J = 10.9, 2.1 Hz, 1H), 0.33 (s, 9H), -0.73 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 176.2, 175.7, 144.9, 139.5, 135.6, 131.6, 131.5, 129.2, 127.2, 125.5, 125.4, 125.0, 123.0 (q, J = 280.1 Hz), 51.3, 50.8, 50.1, 45.9, 45.2, 41.3, 39.6 (q, J = 36.3 Hz), 38.7, 1.9, -1.2; HRMS (ESI-TOF) m/z: calcd for C27H34F3NNaO2Si2+: 540.1972 (M + Na)+, found: 540.1972. 2-Allyl-5-(trimethylsilyl)-6-(2-(trimethylsilyl)naphthalen-1yl)hexahydro-1H-4,7-methanoisoindole-1,3(2H)-dione (4g) (39.6 mg, 83%) was prepared from typical procedure (ethyl acetate : hexane = 1 : 10) as white solid. mp 217-218 ℃. 1H NMR (500 MHz, CDCl3) δ 8.51 (d, J = 8.4 Hz, 1H), 7.81 – 7.78 (m, 1H), 7.68 (d, J = 8.3 Hz, 1H), 7.58 – 7.55 (m, 1H), 7.44 – 7.38 (m, 2H), 5.86 – 5.77 (m, 1H), 5.30 – 5.25 (m, 1H), 5.21 (dd, J = 10.2, 1.1 Hz, 1H), 4.17 (d, J = 6.0 Hz, 2H), 3.94 (s, 1H), 3.66 (d, J = 10.8 Hz, 1H), 3.41 – 3.37 (m, 2H), 2.82 (d, J = 2.0 Hz, 1H), 2.77 (d, J = 10.5 Hz, 1H), 2.02 (d, J = 10.3 Hz, 1H), 1.64 (dd, J = 10.9, 2.2 Hz, 1H), 0.34 (s, 9H), -0.76 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 177.4, 176.8, 145.3, 139.7, 135.5, 131.7, 131.6, 130.7, 129.2, 127.0, 125.5, 125.4, 124.9, 118.7, 51.5, 50.9, 50.1, 45.8, 45.2, 41.4, 41.3, 38.7, 1.9, -1.2; HRMS (ESI-TOF) m/z: calcd for C28H37NNaO2Si2+ : 498.2255 (M + Na)+, found: 498.2255. 2-Allyl-5-(trimethylsilyl)-6-(2-(trimethylsilyl)naphthalen-1yl)hexahydro-1H-4,7-methanoisoindole-1,3(2H)-dione (4h) (28.1 mg, 59%) was prepared from typical procedure (ethyl acetate : hexane = 1 : 10) as white solid. mp 165-166 ℃. 1H NMR (500 MHz, CDCl3) δ 8.32 (d, J = 8.6 Hz, 1H), 7.81 (dd, J = 8.0, 1.5 Hz, 1H), 7.72 (d, J = 8.3 Hz, 1H), 7.57 (d, J = 8.3



Hz, 1H), 7.47 – 7.38 (m, 2H), 5.87 – 5.80 (m, 1H), 5.32 (dq, J = 17.1, 1.3 Hz, 1H), 5.24 (dd, J = 10.2, 1.1 Hz, 1H), 4.14 (d, J = 6.2 Hz, 2H), 3.87 (d, J = 10.9 Hz, 1H), 3.63 (s, 1H), 3.01 (d, J = 7.0 Hz, 1H), 2.92 (d, J = 7.0 Hz, 1H), 2.84 (s, 1H), 2.38 (d, J = 11.6 Hz, 1H), 1.58 (dd, J = 10.9, 2.0 Hz, 1H), 1.49 (d, J = 11.5 Hz, 1H), 0.43 (s, 9H), -0.70 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 178.0, 177.4, 145.5, 139.5, 135.3, 131.7, 131.4, 130.7, 129.0, 126.9, 125.8, 125.6, 125.0, 119.1, 53.2, 52.1, 51.2, 44.7, 43.3, 42.9, 41.0, 35.1, 2.2, -1.2; HRMS (ESI-TOF) m/z: calcd for C28H37NNaO2Si2+: 498.2255 (M + Na)+, found: 498.2255. Trimethyl(1-((1R,2S,3S,4S)-3(trimethylsilyl)bicyclo[2.2.1]hept-5-en-2-yl)naphthalen-2yl)silane (4i) (25.5 mg, 70%) was prepared from typical procedure (ethyl acetate : hexane = 1 : 100) as white solid, mp 7071 ℃. 1H NMR (500 MHz, CDCl3) δ 8.49 (d, J = 8.6 Hz, 1H), 7.80 (dd, J = 8.0, 1.4 Hz, 1H), 7.68 (d, J = 8.2 Hz, 1H), 7.54 (d, J = 8.2 Hz, 1H), 7.44 – 7.36 (m, 2H), 6.52 (dd, J = 5.5, 3.2 Hz, 1H), 6.17 (dd, J = 5.5, 2.8 Hz, 1H), 3.67 (d, J = 10.7 Hz, 1H), 3.56 (d, J = 1.1 Hz, 1H), 3.05 (s, 1H), 2.33 (d, J = 8.5 Hz, 1H), 1.76 (d, J = 8.4 Hz, 1H), 1.12 – 1.07 (m, 1H), 0.33 (s, 9H), 0.71 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 147.4, 139.9, 138.9, 136.6, 135.3, 132.3, 131.4, 128.7, 126.1, 126.0, 125.5, 124.6, 52.8, 49.0, 47.4, 44.4, 34.0, 1.7, -1.2; HRMS (ESI-TOF) m/z: calcd for C23H32NaSi2+: 387.1935 (M + Na)+, found: 387.1937. (3,6-bis(2-(Trimethylsilyl) naphthalen-1yl)bicyclo[2.2.1]heptane-2,5-diyl)bis(trimethylsilane) (4i') (33.8 mg, 53%) was prepared from typical procedure (ethyl acetate : hexane = 1 : 100) as white solid. mp 259-260 ℃. 1H NMR (500 MHz, CDCl3) δ 8.72 (d, J = 8.2 Hz, 2H), 7.86 – 7.82 (m, 2H), 7.72 (d, J = 8.2 Hz, 2H), 7.60 (d, J = 8.2 Hz, 2H), 7.51 – 7.44 (m, 4H), 4.20 (d, J = 10.8 Hz, 2H), 3.33 (s, 2H), 2.83 (s, 2H), 1.79 (d, J = 10.9 Hz, 2H), 0.51 (s, 18H), 0.72 (s, 18H); 13C NMR (126 MHz, CDCl3) δ 148.2, 138.9, 135.7, 132.2, 131.4, 128.9, 126.5, 125.5, 124.6, 59.4, 48.4, 45.6, 42.2, 2.2, -1.2; HRMS (ESI-TOF) m/z: calcd for C39H56NaSi4+: 659.3351 (M + Na)+, found: 659.3351. (3,5-bis(2-(Trimethylsilyl)naphthalen-1yl)bicyclo[2.2.1]heptane-2,6-diyl)bis(trimethylsilane) (4i") (21.7 mg, 34%) was prepared from typical procedure (ethyl acetate : hexane = 1 : 100) as white solid. mp 236-238 ℃. 1H NMR (500 MHz, CDCl3) δ 8.90 (d, J = 8.9 Hz, 2H), 7.84 (dd, J = 8.0, 1.1 Hz, 2H), 7.72 (d, J = 8.2 Hz, 2H), 7.64 (d, J = 8.2 Hz, 2H), 7.57 – 7.53 (m, 2H), 7.49 (t, J = 7.3 Hz, 2H), 4.30 (s, 1H), 4.25 (d, J = 10.9 Hz, 2H), 2.79 (s, 2H), 2.48 (s, 1H), 1.78 (d, J = 10.9 Hz, 2H), 0.54 (s, 18H), -0.62 (s, 18H); 13C NMR (126 MHz, CDCl3) δ 147.3, 139.5, 135.5, 131.9, 131.5, 128.9, 126.5, 126.5, 125.3, 124.6, 59.1, 49.7, 47.8, 43.0, 41.2, 2.8, 0.6; HRMS (ESI-TOF) m/z: calcd for C39H56NaSi4+: 659.3351 (M + Na)+, found: 659.3351. Dimethyl-5-(trimethylsilyl)-6-(2-(trimethylsilyl)naphthalen1-yl)-7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylate (4j) (27.1, 56%) was prepared from typical procedure (ethyl acetate : hexane = 1 : 10) as white solid. mp 118-119 ℃. 1H NMR (500 MHz, CDCl3) δ 9.00 – 8.97 (m, 1H), 7.81 – 7.78 (m, 1H), 7.72 (d, J = 8.3 Hz, 1H), 7.56 (d, J = 8.3 Hz, 1H), 7.48 – 7.43 (m, 2H), 5.35 (s, 1H), 5.03 (d, J = 5.7 Hz, 1H), 4.07 (d, J = 11.2 Hz, 1H), 3.91 (dd, J = 5.6, 4.0 Hz, 1H), 3.78 (s, 3H), 3.69 (s, 3H), 3.46 (d, J = 4.0 Hz, 1H), 1.68 (d, J = 11.2 Hz, 1H), 0.45 (s, 9H), -0.52 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 172.5, 171.8, 144.7, 139.3, 135.1, 131.6, 130.7, 128.5, 127.6, 127.0,

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126.0, 125.6, 85.5, 80.6, 53.8, 53.3, 52.4, 52.4, 52.2, 39.1, 1.3, -1.4; HRMS (ESI-TOF) m/z: calcd for C26H36NaO5Si2+: 507.1993 (M + Na)+, found: 507.1994. Dimethyl-5-(trimethylsilyl)-6-(2-(trimethylsilyl)naphthalen1-yl)-7-oxabicyclo[2.2.1]hept-2-ene-2,3-dicarboxylate (4k) (21.8 mg, 45%) was prepared from typical procedure (with ethyl acetate : hexane = 1 : 10) as white solid. mp 115-116 ℃. 1 H NMR (500 MHz, CDCl3) δ 8.90 (dd, J = 8.4, 1.0 Hz, 1H), 7.83 – 7.80 (m, 1H), 7.74 (d, J = 8.3 Hz, 1H), 7.59 – 7.56 (m, 1H), 7.49 – 7.42 (m, 2H), 5.76 (d, J = 0.7 Hz, 1H), 5.40 (d, J = 1.3 Hz, 1H), 3.89 (s, 3H), 3.76 (s, 3H), 1.60 (d, J = 10.5 Hz, 2H), 0.32 (s, 9H), -0.45 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 163.4, 162.0, 145.1, 143.3, 143.2, 140.1, 135.0, 131.8, 130.9, 128.5, 127.2, 127.1, 126.1, 125.6, 84.8, 83.4, 52.4, 52.1, 51.1, 32.3, 1.4, -1.3; HRMS (ESI-TOF) m/z: calcd for C26H34NaO5Si2+: 505.1837(M + Na)+, found: 505.1837. Trimethyl(1-(3-(trimethylsilyl)-1,2,3,4-tetrahydro-1,4epoxynaphthalen-2-yl) naphthalen-2-yl) silane (4l) (37.5 mg, 90%) was prepared from typical procedure (ethyl acetate : hexane = 1 : 100) as white solid. mp 119-121 ℃. 1H NMR (500 MHz, CDCl3) δ 9.21 – 9.17 (m, 1H), 7.84 – 7.80 (m, 1H), 7.73 (d, J = 8.3 Hz, 1H), 7.53 (d, J = 8.3 Hz, 1H), 7.51 – 7.47 (m, 2H), 7.29 (d, J = 7.5 Hz, 2H), 7.24 – 7.17 (m, 2H), 5.80 (s, 1H), 5.59 (s, 1H), 3.88 (d, J = 10.7 Hz, 1H), 1.49 (d, J = 10.7 Hz, 1H), 0.14 (s, 9H), -0.43 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 146.9, 146.6, 145.1, 139.5 , 135.0, 132.1, 130.7, 128.4, 127.9, 126.8, 126.7, 126.2, 126.1, 125.6, 118.4, 118.1, 83.5, 81.6, 53.1, 37.2, 1.3, -1.0; HRMS (ESI-TOF) m/z: calcd for C26H32KOSi2+: 455.1623 (M + K)+, found: 455.1628. tert-Butyl -2-(trimethylsilyl)-3-(2-(trimethylsilyl) naphthalen-1-yl)-1,2,3,4-tetrahydro-1,4-epiminonaphthalene-9carboxylate (4m) (45.9 mg, 89%). White solid. mp 168-169 ℃. (ethyl acetate : hexane = 1 : 40). 1H NMR (500 MHz, CDCl3) δ 9.02 (s, 1H), 7.82 (d, J = 7.9 Hz, 1H), 7.73 (d, J = 8.3 Hz, 1H), 7.53 (d, J = 8.3 Hz, 1H), 7.51 – 7.42 (m, 2H), 7.29 (dd, J = 25.3, 6.5 Hz, 2H), 7.22 – 7.13 (m, 2H), 5.50 (s, 1H), 5.28 (s, 1H), 3.78 (d, J = 10.7 Hz, 1H), 1.44 (s, 9H), 1.38 (d, J = 10.7 Hz, 1H), 0.10 (s, 9H), -0.46 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 155.2, 147.5, 146.4, 145.2, 139.7, 135.1, 132.4, 130.9, 128.4, 128.0, 126.9, 126.7, 126.1, 126.0, 125.2, 119.9, 118.7, 80.3, 66.6, 63.4, 54.2, 36.1, 28.4, 1.3, -1.3; HRMS (ESI-TOF) m/z: calcd for C31H41NO2Si2Na+: 538.2568 (M + Na)+, found: 538.2563. 9-tosyl-2-(trimethylsilyl)-3-(2 (trimethylsilyl)naphthalen-1yl)-1,2,3,4-tetrahydro-1,4-epiminonaphthalene (4n) (56.9 mg, 99%) was prepared from typical procedure (ethyl acetate : hexane = 1 : 100) as white solid. mp 222-223 ℃. 1H NMR (500 MHz, CDCl3) δ 9.44 (d, J = 8.6 Hz, 1H), 7.82 (dd, J = 8.2, 1.1 Hz, 1H), 7.73 (d, J = 8.2 Hz, 1H), 7.66 – 7.61 (m, 1H), 7.56 – 7.52 (m, 1H), 7.50 (d, J = 8.3 Hz, 1H), 7.35 (d, J = 8.3 Hz, 2H), 7.00 (d, J = 7.2 Hz, 1H), 6.95 – 6.90 (m, 3H), 6.81 (td, J = 7.4, 1.0 Hz, 1H), 6.74 (d, J = 7.2 Hz, 1H), 5.37 (s, 1H), 5.28 (s, 1H), 3.76 (d, J = 10.8 Hz, 1H), 2.25 (s, 3H), 1.38 (d, J = 10.8 Hz, 1H), 0.02 (s, 9H), -0.38 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 146.0, 144.0, 143.2, 142.8, 139.5, 134.9, 134.8, 132.3, 130.7, 128.9, 128.7, 128.3, 128.1, 127.1, 126.6, 126.5, 126.0, 125.8, 119.8, 119.0, 68.1, 66.6, 55.0, 36.9, 21.4, 1.2, -1.2; HRMS (ESI-TOF) m/z: calcd for C33H39NNaO2SSi2+: 592.2132 (M + Na)+, found: 592.2132. Procedure for the Preparation of 5. A dried 10 mL Schlenk tube was charged with 1-fluoro-2-iodobenzene 1b (22.2 mg, 0.1 mmol), hexamethyldisilane 2a (22 mg, 0.15 mmol, 1.5


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equiv), 1,4-epoxy-1,4-dihydronaphthalene 3l (28.8 mg, 0.2 mmol, 2 equiv), Pd(OAc)2 (2.3 mg, 0.01 mmol, 10 mol %), PPh3 (5.3 mg, 0.02 mmol, 20 mol %), Cs2CO3 (66 mg, 0.2 mmol, 2 equiv), and DMF (1 mL) and then the tube was evacuated and back filled with nitrogen (10 times). The reaction mixture was heated to 100 °C for 12 hours under vigorous stirring. Upon completion, the reaction mixture was cooled to room temperature, diluted with ethyl acetate, and filtered through a pad of celite. The filtrate was concentrated under vacuum, and the resulting residue was purified by preparative thin layer chromatography (PTLC) with ethyl acetate : hexane = 1 : 100 to give the corresponding products (3-fluoro-2-(3(trimethylsilyl)-1,2,3,4-tetrahydro-1,4-epoxynaphthalen-2yl)phenyl)trimethylsilane (5a) (33.5 mg, 87%) as a colorless oil. 1H NMR (500 MHz, CDCl3) δ 7.25 – 7.20 (m, 4H), 7.20 – 7.13 (m, 2H), 7.10 – 7.05 (m, 1H), 5.57 (d, J = 2.2 Hz, 1H), 5.43 (s, 1H), 3.30 (d, J = 10.2 Hz, 1H), 1.32 (d, J = 10.2 Hz, 1H), 0.13 (s, 9H), -0.21 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 161.00 (d, J = 251.8 Hz), 147.0, 146.7 (d, J = 2.1 Hz), 143.9 (d, J = 2.2 Hz), 133. 8 (d, J = 11.8 Hz), 130.2 (d, J = 3.2 Hz), 127.9 (d, J = 7.6 Hz), 126.6, 126.2, 118.2, 118.0, 117.9, 83.5 (d, J = 2.4 Hz), 80.9, 48.6 (d, J = 2.9 Hz), 37.3, 0.8, -1.5 (d, J = 2.4 Hz); HRMS (ESI-TOF) m/z: calcd for C22H29FNaOSi2+: 407.1633 (M + Na)+, found: 407.1634. (3-Chloro-2-(3-(trimethylsilyl)-1,2,3,4-tetrahydro-1,4epoxynaphthalen-2-yl)phenyl)trimethylsilane (5b) (36.9 mg, 92%). White solid, mp 92-93 ℃, was prepared from typical procedure at 60 ℃ for 12 h. 1H NMR (500 MHz, CDCl3) δ 7.39 (dd, J = 7.9, 1.3 Hz, 1H), 7.35 (dd, J = 7.4, 1.4 Hz, 1H), 7.25 – 7.21 (m, 2H), 7.19 – 7.13 (m, 3H), 5.93 (s, 1H), 5.42 (s, 1H), 3.50 (d, J = 10.5 Hz, 1H), 1.36 (d, J = 10.5 Hz, 1H), 0.08 (s, 9H), -0.19 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 146.9, 146.8, 145.1, 143.7, 133.3, 133.2, 133.2, 127.4, 126.6, 126.2, 118.3, 117.8, 81.6, 80.6, 52.1, 37.7, 1.1, -1.0; HRMS (ESITOF) m/z: calcd for C22H29ClNaOSi2+: 423.1338 (M + Na)+, found: 423.1338. Trimethyl(3-methyl-2-(3-(trimethylsilyl)-1,2,3,4-tetrahydro1,4-epoxynaphthalen-2-yl)phenyl) silane (5c) (29.7 mg, 78%). White solid. mp 104-105 ℃ 1H NMR (500 MHz, CDCl3) δ 7.30 (dd, J = 7.2, 1.1 Hz, 1H), 7.25 – 7.21 (m, 2H), 7.20 – 7.17 (m, 2H), 7.17 – 7.11 (m, 2H), 5.64 (s, 1H), 5.41 (s, 1H), 3.54 (d, J = 10.5 Hz, 1H), 2.67 (s, 3H), 1.38 (d, J = 10.5 Hz, 1H), 0.07 (s, 9H), -0.26 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 146.8, 146.5, 144.8, 142.3, 136.4, 134.2, 132.8, 126.6, 126.2, 126.2, 118.2, 118.0, 81.9, 80.5, 52.2, 37.9, 22.0, 1.3, -1.1; HRMS (ESI-TOF) m/z: calcd for C23H32NaOSi2+: 403.1884 (M + Na)+, found: 403.1884. (3-Methoxy-2-(3-(trimethylsilyl)-1,2,3,4-tetrahydro-1,4epoxynaphthalen-2-yl)phenyl)trimethylsilane (5d) (35.4 mg, 89%). White solid. mp 117-118 ℃. 1H NMR (500 MHz, CDCl3) δ 7.24 – 7.17 (m, 3H), 7.17 – 7.10 (m, 2H), 7.04 (dd, J = 7.4, 1.1 Hz, 1H), 6.89 (d, J = 8.1 Hz, 1H), 5.61 (s, 1H), 5.38 (s, 1H), 3.79 (s, 3H), 3.31 (d, J = 10.3 Hz, 1H), 1.28 (s, 1H), 0.08 (s, 9H), -0.25 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 157.9, 147.9, 146.7, 142.8, 134.4, 127.3, 126.54, 126.2, 125.9, 118.2, 117.6, 111.9, 82.9, 80.8, 54.2, 50.2, 36.6, 1.0, -1.4; HRMS (ESI-TOF) m/z: calcd for C23H32NaO2Si2+: 419.1833 (M + Na)+, found: 419.1832. (3-(Methoxymethyl)-2-(3-(trimethylsilyl)-1,2,3,4tetrahydro-1,4-epoxynaphthalen-2-yl)phenyl)trimethylsilane (5e) (21.3 mg, 52%). Colorless oil. 1H NMR (500 MHz, CDCl3) 1H NMR (500 MHz, CDCl3) δ 7.47 – 7.43 (m, 2H),

7.30 – 7.28 (m, 1H), 7.28 – 7.24 (m, 2H), 7.23 – 7.17 (m, 2H), 5.87 (s, 1H), 5.44 (s, 1H), 5.36 (d, J = 10.0 Hz, 1H), 4.25 (d, J = 10.0 Hz, 1H), 3.57 (d, J = 10.5 Hz, 1H), 3.51 (s, 3H), 1.43 (d, J = 10.5 Hz, 1H), 0.10 (s, 9H), -0.28 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 146.8, 146.6, 146.5, 142.9, 135.9, 135.2, 134.6, 126.6, 126.5, 126.3, 118.3, 118.1, 83.1, 80.4, 74.0, 58.1, 52.0, 38.1, 1.3, -1.3; HRMS (ESI-TOF) m/z: calcd for C24H34NaO2Si2+: 433.1990 (M + Na)+, found: 433.1991. Methyl 2-methyl-4-(trimethylsilyl)-3-(3-(trimethylsilyl)1,2,3,4-tetrahydro-1,4-epoxynaphthalen-2-yl)benzoate (5f) (34.7 mg, 79%). Colorless oil. (ethyl acetate : hexane = 1 : 10). 1 H NMR (500 MHz, CDCl3) δ 7.47 (d, J = 7.7 Hz, 1H), 7.34 (d, J = 7.7 Hz, 1H), 7.24 (t, J = 6.6 Hz, 2H), 7.21 – 7.14 (m, 2H), 5.62 (s, 1H), 5.44 (s, 1H), 3.90 (s, 3H), 3.58 (d, J = 10.6 Hz, 1H), 2.77 (s, 3H), 1.40 (d, J = 10.6 Hz, 1H), 0.06 (s, 9H), 0.24 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 169.9, 146.5, 146.5, 146.5, 146.4, 135.9, 135.2, 132.2, 126.7, 126.7, 126.2, 118.3, 118.0, 82.1, 80.7, 53.0, 52.1, 37.6, 18.4, 1.0, -1.0; HRMS (ESI-TOF) m/z: calcd for C25H34NaO3Si2+: 461.1939 (M + Na)+, found: 461.1939. Methyl 3-methyl-5-(trimethylsilyl)-4-(3-(trimethylsilyl)1,2,3,4-tetrahydro-1,4-epoxynaphthalen-2-yl)benzoate (5g) (36.4 mg, 83%). White solid. mp 143-144 ℃. (ethyl acetate : hexane = 1 : 10). 1H NMR (500 MHz, CDCl3) δ 7.95 (d, J = 1.9 Hz, 1H), 7.85 (d, J = 1.8 Hz, 1H), 7.26 – 7.22 (m, 2H), 7.22 – 7.15 (m, 2H), 5.65 (s, 1H), 5.42 (s, 1H), 3.91 (s, 3H), 3.58 (d, J = 10.6 Hz, 1H), 2.72 (s, 3H), 1.40 (d, J = 10.6 Hz, 1H), 0.10 (s, 9H), -0.27 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 167.4, 150.7, 146.8, 146.1, 143.1, 136.7, 135.1, 133.5, 127.5, 126.8, 126.4, 118.2, 118.1, 81.6, 80.5, 52.4, 52.0, 38.2, 22.0, 1.1, -1.0; HRMS (ESI-TOF) m/z: calcd for C25H34NaO3Si2+: 461.1939 (M + Na)+, found: 461.1937. N-Methoxy-N,3-dimethyl-5-(trimethylsilyl)-4-(3(trimethylsilyl)-1,2,3,4-tetrahydro-1,4-epoxynaphthalen-2yl)benzamide (5h) (41.6 mg, 88%). White solid. mp 137138 ℃. (ethyl acetate : hexane = 1 : 4). 1H NMR (500 MHz, CDCl3) δ 7.60 (d, J = 1.7 Hz, 1H), 7.50 (d, J = 1.6 Hz, 1H), 7.28 – 7.25 (m, 1H), 7.24 – 7.21 (m, 1H), 7.21 – 7.15 (m, 2H), 5.65 (s, 1H), 5.42 (s, 1H), 3.56 (d, J = 10.6 Hz, 1H), 3.54 (s, 3H), 3.35 (s, 3H), 2.70 (s, 3H), 1.40 (d, J = 10.5 Hz, 1H), 0.09 (s, 9H), -0.25 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 170.2, 147.8, 146.7, 146.2, 142.3, 136.1, 133.7, 132.1, 131.7, 126.8, 126.3, 118.2, 118.0, 81.6, 80.4, 61.0), 52.3, 38.2, 22.0, 1.2, 1.0; HRMS (ESI-TOF) m/z: calcd for C26H37NNaO3Si2+: 490.2204 (M + Na)+, found: 490.2204. Trimethyl(4-methyl-2-(3-(trimethylsilyl)-1,2,3,4-tetrahydro1,4-epoxynaphthalen-2-yl)phenyl)silane (5i) (21.7 mg, 57%). White solid. mp 119-121 ℃. 1H NMR (500 MHz, CDCl3) δ 7.56 (s, 1H), 7.31 (d, J = 7.6 Hz, 1H), 7.25 (t, J = 5.8 Hz, 2H), 7.21 – 7.14 (m, 2H), 7.04 (dd, J = 7.6, 0.9 Hz, 1H), 5.40 (s, 1H), 5.34 (s, 1H), 3.21 (d, J = 9.6 Hz, 1H), 2.35 (s, 3H), 1.32 (d, J = 9.6 Hz, 1H), 0.17 (s, 9H), -0.23 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 149.8, 147.9, 145.6, 139.4, 135.2, 134.1, 128.8, 126.6, 126.6, 126.2, 118.5, 117.8, 86.8, 80.5, 48.4, 38.5, 21.3, 0.7, -1.2; HRMS (ESI-TOF) m/z: calcd for C23H32NaOSi2+: 403.1884 (M + Na)+ , found: 403.1882. (4-Methoxy-2-(3-(trimethylsilyl)-1,2,3,4-tetrahydro-1,4epoxynaphthalen-2-yl)phenyl)trimethylsilane (5j) (21.0 mg, 53%). White solid. mp 123-124 ℃. 1H NMR (500 MHz, CDCl3) δ 7.34 (d, J = 5.7 Hz, 1H), 7.33 (s, 1H), 7.25 (dd, J = 8.7, 5.1 Hz, 2H), 7.21 – 7.15 (m, 2H), 6.77 (dd, J = 8.3, 2.6 Hz, 1H), 5.39 (s, 1H), 5.34 (s, 1H), 3.84 (s, 3H), 3.23 (d, J = 9.6



Hz, 1H), 1.32 (d, J = 9.6 Hz, 1H), 0.16 (s, 9H), -0.19 (s, 9H); 13 C NMR (126 MHz, CDCl3) δ 161.0, 151.8, 147.9, 145.5, 135.4, 130.0, 126.6, 126.2, 118.6, 117.8, 113.6, 111.5, 86.7, 80.5, 55.1, 48.5, 38.4, 0.7, -1.1; HRMS (ESI-TOF) m/z: calcd for C23H32NaO2Si2+: 419.1833 (M + Na)+, found: 419.1831. Trimethyl(5-methyl-2-(3-(trimethylsilyl)-1,2,3,4-tetrahydro1,4-epoxynaphthalen-2-yl)phenyl)silane (5k) (25.6 mg, 67%). Colorless oil. 1H NMR (500 MHz, CDCl3) δ 7.63 (d, J = 7.9 Hz, 1H), 7.24 (dd, J = 7.4, 4.4 Hz, 2H), 7.22 – 7.14 (m, 4H), 5.39 (s, 1H), 5.29 (s, 1H), 3.21 (d, J = 9.6 Hz, 1H), 2.34 (s, 3H), 1.32 (d, J = 9.6 Hz, 1H), 0.18 (s, 9H), -0.22 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 147.9, 146.8, 145.6, 138.7, 135.0, 134.6, 130.4, 127.9, 126.6, 126.2, 118.5, 117.8, 87.0, 80.5, 48.1, 38.3, 21.2, 0.7, -1.0; HRMS (ESI-TOF) m/z: calcd for C23H32NaOSi2+: 403.1884 (M + Na)+, found: 403.1882. (5-Methoxy-2-(3-(trimethylsilyl)-1,2,3,4-tetrahydro-1,4epoxynaphthalen-2-yl)phenyl)trimethylsilane (5l) (30.9 mg, 78%). White solid. mp 87-88 ℃. 1H NMR (500 MHz, CDCl3) δ 7.67 (d, J = 8.6 Hz, 1H), 7.26 – 7.24 (m, 1H), 7.23 (s, 1H), 7.21 – 7.13 (m, 2H), 6.97 (d, J = 2.9 Hz, 1H), 6.92 (dd, J = 8.6, 2.9 Hz, 1H), 5.39 (s, 1H), 5.27 (s, 1H), 3.82 (s, 3H), 3.20 (d, J = 9.5 Hz, 1H), 1.31 (d, J = 9.5 Hz, 1H), 0.19 (s, 9H), -0.20 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 157.5, 147.9, 145.6, 141.8, 140.4, 129.1, 126.6, 126.2, 119.8, 118.6, 117.8, 114.2, 87.0, 80.6, 55.2, 47.7, 38.3, 0.5, -1.0; HRMS (ESI-TOF) m/z: calcd for C23H32NaO2Si2+: 419.1833 (M + Na)+, found: 419.1834. Trimethyl(5-(trifluoromethoxy)-2-(3-(trimethylsilyl)1,2,3,4-tetrahydro-1,4-epoxynaphthalen-2-yl)phenyl)silane (5m) (25.8 mg, 57%). White solid. mp 155-156 ℃. 1H NMR (500 MHz, CDCl3) δ 7.80 – 7.75 (m, 1H), 7.28 – 7.24 (m, 2H), 7.23 – 7.16 (m, 4H), 5.40 (s, 1H), 5.29 (s, 1H), 3.24 (d, J = 9.6 Hz, 1H), 1.33 (d, J = 9.6 Hz, 1H), 0.21 (s, 9H), -0.21 (s, 9H); 13 C NMR (126 MHz, CDCl3) δ 148.6, 147.8, 147.6 (q, J = 1.6 Hz), 145.2, 141.6, 129.4, 126.8, 126.4, 126.0, 121.8, 120.5 (q, J = 256.5 Hz), 118.6, 117.9, 86.7, 80.6, 48.1, 38.6, 0.3, -1.1; HRMS (ESI-TOF) m/z: calcd for C23H29F3NaO2Si2+: 473.1550 (M + Na)+, found: 473.1551. N-(3-(Trimethylsilyl)-4-(3-(trimethylsilyl)-1,2,3,4tetrahydro-1,4-epoxynaphthalen-2-yl)phenyl)acetamide (5n) (26.7 mg, 63%). White solid. mp 213-214 ℃. (ethyl acetate : hexane = 1 : 4). 1H NMR (500 MHz, CDCl3) δ 7.70 (d, J = 8.5 Hz, 1H), 7.63 (dd, J = 8.5, 2.3 Hz, 1H), 7.46 (d, J = 2.3 Hz, 1H), 7.35 (s, 1H), 7.26 – 7.22 (m, 2H), 7.21 – 7.14 (m, 2H), 5.39 (s, 1H), 5.27 (s, 1H), 3.21 (d, J = 9.6 Hz, 1H), 2.17 (s, 3H), 1.32 (d, J = 9.6 Hz, 1H), 0.19 (s, 9H), -0.21 (s, 9H);13C NMR (126 MHz, CDCl3) δ 168.2, 147.9, 145.7, 145.4, 139.8, 135.8, 128.5, 126.6, 126.2, 124.9, 121.1, 118.6, 117.8, 86.8, 80.5, 48.1, 38.4, 24.6, 0.5, -1.01; HRMS (ESI-TOF) m/z: calcd for C24H33NNaO2Si2+: 446.1942 (M + Na)+,found: 446.1942. (5-Fluoro-2-(3-(trimethylsilyl)-1,2,3,4-tetrahydro-1,4epoxynaphthalen-2-yl)phenyl)trimethylsilane (5o) (23.8 mg, 62%). White solid. mp 112-114 ℃. 1H NMR (500 MHz, CDCl3) δ 7.74 (dd, J = 8.6, 5.5 Hz, 1H), 7.28 (t, J = 7.8 Hz, 2H), 7.25 – 7.18 (m, 2H), 7.14 – 7.06 (m, 2H), 5.42 (s, 1H), 5.30 (s, 1H), 3.25 (d, J = 9.6 Hz, 1H), 1.35 (d, J = 9.5 Hz, 1H), 0.23 (s, 9H), -0.18 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 161.3 (d, J = 246.7 Hz), 147.9, 145.4 (d, J = 3.1 Hz), 145.3, 141.7 (d, J = 3.4 Hz), 129.6 (d, J = 6.8 Hz), 126.7, 126.3, 120.1 (d, J = 18.6 Hz), 118.6, 117.9, 116.2 (d, J = 20.7 Hz), 86.9, 80.6, 47.9, 38.4, 0.4, -1.1; HRMS (ESI-TOF) m/z: calcd for C22H29FNaOSi2+: 407.1633 (M + Na)+, found: 407.1634.

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(3-(Trimethylsilyl)-4-(3-(trimethylsilyl)-1,2,3,4-tetrahydro1,4-epoxynaphthalen-2-yl)phenyl)methanol (5p) (17.9 mg, 45%). Colorless oil. ethyl acetate : hexane = 1 : 5. 1H NMR (500 MHz, CDCl3) δ 7.75 (d, J = 7.9 Hz, 1H), 7.39 (d, J = 7.8 Hz, 2H), 7.26 – 7.24 (m, 2H), 7.22 – 7.15 (m, 2H), 5.40 (s, 1H), 5.29 (s, 1H), 4.69 (s, 2H), 3.25 (d, J = 9.6 Hz, 1H), 1.33 (d, J = 9.6 Hz, 1H), 0.20 (s, 9H), -0.22 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 149.5, 147.9, 145.4, 139.2, 138.1, 132.8, 128.5, 128.2, 126.7, 126.3, 118.6, 117.9, 86.9, 80.5, 65.5, 48.4, 38.4, 0.6, -1.0; HRMS (ESI-TOF) m/z: calcd for C23H32NaO2Si2 +: 419.1833 (M + Na)+, found: 419.1837. Trimethyl(2-(3-(trimethylsilyl)-1,2,3,4-tetrahydro-1,4epoxynaphthalen-2-yl)phenyl)silane (5q) (22.4 mg, 61%). Colorless oil. 1H NMR (500 MHz, CDCl3) δ 7.74 (dd, J = 7.8, 0.6 Hz, 1H), 7.42 (dd, J = 7.4, 1.2 Hz, 1H), 7.38 (td, J = 7.6, 1.4 Hz, 1H), 7.28 – 7.15 (m, 5H), 5.40 (s, 1H), 5.33 (s, 1H), 3.24 (d, J = 9.6 Hz, 1H), 1.34 (d, J = 9.6 Hz, 1H), 0.19 (s, 9H), -0.22 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 149.9, 147.9, 145.6, 138.8, 133.9, 129.7, 127.9, 126.6, 126.2, 125.8, 118.6, 117.9, 86.8, 80.5, 48.6, 38.4, 0.61, -1.1; HRMS (ESI-TOF) m/z: calcd for C22H30NaOSi2+: 389.1727 (M + Na)+, found: 389.1725 Trimethyl(2-(3-(trimethylsilyl)-1,2,3,4-tetrahydro-1,4epoxynaphthalen-2-yl)thiophen-3-yl)silane (5r) (18.2 mg, 49%). Colorless oil. 1H NMR (500 MHz, CDCl3) δ 7.27 (d, J = 6.8 Hz, 1H), 7.24 – 7.15 (m, 4H), 6.94 (d, J = 5.1 Hz, 1H), 5.38 (s, 1H), 5.30 (s, 1H), 3.59 (dd, J = 9.4, 0.6 Hz, 1H), 1.32 (d, J = 9.4 Hz, 1H), 0.20 (s, 9H), -0.09 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 154.4, 147.7, 144.5, 137.0, 131.6, 126.9, 126.3, 123.8, 119.0, 117.7, 87.1, 81.0, 45.8, 37.7, 0.4, -1.1; HRMS (ESI-TOF) m/z: calcd for C20H28NaOSSi2+: 395.1292 (M + Na)+, found: 395.1293. Methyl 2-((tert-butoxycarbonyl)amino)-3-(3(trimethylsilyl)-4-(3-(trimethylsilyl)-1,2,3,4-tetrahydro-1,4epoxynaphthalen-2-yl)phenyl)propanoate (5s) (28.9 mg, 51%). White solid. mp 138-139 ℃. 1H NMR (500 MHz, CDCl3) δ 7.66 (d, J = 7.8 Hz, 1H), 7.24 (d, J = 8.2 Hz, 2H), 7.21 – 7.16 (m, 2H), 7.13 (d, J = 1.8 Hz, 2H), 5.39 (s, 1H), 5.30 (s, 1H), 4.93 (dd, J = 27.4, 8.0 Hz, 1H), 4.58 (dd, J = 12.8, 5.7 Hz, 1H), 3.71 (d, J = 6.1 Hz, 3H), 3.21 (d, J = 9.5 Hz, 1H), 3.09 (qd, J = 13.6, 7.1 Hz, 2H), 1.44 (s, 9H), 1.32 (d, J = 9.6 Hz, 1H), 0.18 (s, 10H), -0.23 (d, J = 2.2 Hz, 11H); 13C NMR (126 MHz, CDCl3) δ 172.23, 172.20, 154.92, 154.90, 148.68, 148.67, 147.9, 145.5, 139.1, 139.0, 134.9, 134.8, 133.12, 133.05, 130.7, 130.6, 128.2, 128.1, 126.7, 126.2, 118.6, 117.9, 86.7, 80.5, 79.82, 79.78, 54.4, 54.3, 52.2, 52.1, 48.2, 38.5, 37.8, 37.7, 28.3, 0.6, -1.06, -1.08; HRMS (ESI-TOF) m/z: calcd for C31H45NNaO5Si2+: 590.2728 (M + Na)+, found: 590.2729. 13-Methyl-2-(trimethylsilyl)-3-(3-(trimethylsilyl)-1,2,3,4tetrahydro-1,4-epoxynaphthalen-2-yl)6,7,8,9,11,12,13,14,15,16-decahydro-17Hcyclopenta[a]phenanthren-17-one (5t) (29.3 mg, 54%). Colorless oil. ethyl acetate : hexane = 1 : 10. 1H NMR (500 MHz, CDCl3) δ 7.48 (d, J = 3.5 Hz, 1H), 7.38 (d, J = 15.7 Hz, 1H), 7.26 (t, J = 7.2 Hz, 2H), 7.24 – 7.17 (m, 2H), 5.42 (s, 1H), 5.35 (s, 1H), 3.21 (dd, J = 9.6, 1.9 Hz, 1H), 3.00 – 2.89 (m, 2H), 2.54 (dd, J = 19.2, 8.7 Hz, 1H), 2.35 (t, J = 8.8 Hz, 1H), 2.22 – 2.14 (m, 1H), 2.13 – 2.09 (m, 1H), 2.04 – 1.99 (m, 1H), 1.72 – 1.43 (m, 8H), 1.34 (d, J = 3.4 Hz, 1H), 0.96 (d, J = 12.9 Hz, 3H), 0.21 (d, J = 3.9 Hz, 9H), -0.20 (d, J = 4.4 Hz, 9H); 13 C NMR (100 MHz, CDCl3) δ 221.01, 220.96, 147.9, 147.8, 147.2, 147.1, 145.7, 145.6, 138.0, 137.8, 137.0, 136.8, 135.7,


Page 9 of 13 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


135.6, 131.1, 130.9, 128.43, 128.37, 126.6, 126.2,118.52, 118.49, 117.9, 117.8, 86.9, 86.8, 80.5, 50.6, 50.5, 48.08, 48.06, 48.04, 48.00, 44.4, 44.3, 38.6, 38.42, 38.36, 38.3, 35.88, 35.86, 31.7, 31.6, 29.4, 29.3, 26.7, 26.4, 26.0, 25.5, 21.6, 14.0, 13.8, 0.74, 0.71, -1.1, -1.2; HRMS (ESI-TOF) m/z: calcd for C34H46NaO2Si2+: 565.2929 (M + Na)+, found: 565.2929. Procedure for the Preparation of 6a. A dried 10 mL Schlenk tube was charged with 1-iodonaphthalene 1a (25.4 mg, 0.10 mmol), 1,1,1,2,2,2-hexamethyldigermane 2b (35.3 mg, 0.15 mmol, 1.5 equiv), norbornene 3a (19 mg, 0.20 mmol, 2.0equiv), Pd(OAc)2 (2.3 mg, 0.01 mmol, 10mol%), PPh3 (5.3 mg, 0.02 mmol, 20mol%), norbornene 3a (19 mg, 0.20 mmol, 2 equiv),Cs2CO3 (66 mg, 0.2 mmol, 2 equiv), and DMF (1 mL) and then the tube was evacuated and back filled with nitrogen (10 times). The reaction mixture was heated to 60 °C for 12 hours under vigorous stirring. Upon completion, the reaction mixture was cooled to room temperature, diluted with ethyl acetate, and filtered through a pad of celite. The filtrate was concentrated under vacuum, and the resulting residue was purified by preparative thin layer chromatography (PTLC) with ethyl acetate : hexane = 1 : 100 to give the corresponding products Trimethyl(1-(3(trimethylgermyl)bicyclo[2.2.1]heptan-2-yl)naphthalen-2yl)germane (6a) (41.5 mg, 91%) as white solid, mp 77-78 ℃. 1 H NMR (500 MHz, CDCl3) δ 8.58 (dd, J = 6.3, 3.5 Hz, 1H), 7.79 (dd, J = 6.2, 3.4 Hz, 1H), 7.66 (d, J = 8.2 Hz, 1H), 7.50 (d, J = 8.2 Hz, 1H), 7.46 – 7.36 (m, 2H), 3.73 (d, J = 10.6 Hz, 1H), 3.07 (d, J = 1.6 Hz, 1H), 2.42 (d, J = 4.3 Hz, 1H), 2.29 (d, J = 9.8 Hz, 1H), 1.96 – 1.88 (m, 1H), 1.74 – 1.62 (m, 2H), 1.59 – 1.54 (m, 2H), 1.48 – 1.41 (m, 1H), 0.53 (s, 9H), -0.60 (s, 9H); 13 C NMR (126 MHz, CDCl3) δ 146.7, 141.7, 135.2, 132.0, 130.7, 128.7, 126.4, 126.2, 125.2, 124.5, 54.7, 47.1, 42.5, 40.1, 39.9, 34.0, 31.8, 1.7, -1.5; HRMS (ESI-TOF) m/z: calcd for C23H34Ge2Na+: 481.0976 (M + Na)+, found: 481.0977. Procedure for the Preparation of 6b. A dried 10 mL Schlenk tube was charged with 1-fluoro-2-iodobenzene 1a (22.3 mg, 0.10 mmol, 1.0equiv), 1,1,1,2,2,2hexamethyldigermane 2b (35.3 mg, 0.15 mmol, 1.5 equiv), 2allyl-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)dione 3g (40.6 mg, 0.2 mmol, 2 equiv), Pd(OAc)2 (2.3 mg, 0.01 mmol, 10mol%), triphenylphosphine (PPh3) (5.3 mg, 0.02 mmol, 20 mol%), Cs2CO3 (66 mg, 0.20 mmol, 2.0equiv), and DMF (1.0 mL) and then the tube was evacuated and back filled with nitrogen (10 times). After stirring at 100 ℃for 12 h, After cooling to room temperature, the reaction mixture was diluted with ethyl acetate (15 mL), washed with H2O (10 ml, 3 times), dried over Na2SO4 and concentrated in vacuo. The residue was purified by preparative thin layer chromatography (PTLC) with ethyl acetate: hexane = 1: 10 to give the corresponding products 2-allyl-5-(naphthalen-1-yl)-6(trimethylgermyl)hexahydro-1H-4,7-methanoisoindole1,3(2H)-dione (6b) (31.7 mg, 56%) as white solid, mp 222223 ℃. 1H NMR (500 MHz, CDCl3) δ 8.53 – 8.48 (m, 1H), 7.82 – 7.77 (m, 1H), 7.66 (d, J = 8.2 Hz, 1H), 7.52 (d, J = 8.2 Hz, 1H), 7.44 – 7.39 (m, 2H), 5.86 – 5.77 (m, 1H), 5.27 (dd, J = 17.1, 1.2 Hz, 1H), 5.21 (dd, J = 10.2, 1.1 Hz, 1H), 4.18 (d, J = 6.0 Hz, 2H), 3.97 (s, 1H), 3.58 (d, J = 10.6 Hz, 1H), 3.42 – 3.36 (m, 2H), 2.81 (d, J = 1.8 Hz, 1H), 2.73 (d, J = 10.4 Hz, 1H), 2.02 (d, J = 10.1 Hz, 1H), 1.88 (dd, J = 10.6, 2.3 Hz, 1H), 0.44 (s, 9H), -0.62 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 177.3, 176.8, 144.0, 142.4, 135.4, 131.6, 131.0, 130.7, 129.3, 127.1, 125.3, 125.2, 125.0, 118.7, 51.5, 50.8, 50.7, 45.6, 44.9,

41.9, 41.3, 40.2, 1.5, -1.5; HRMS (ESI-TOF) m/z: calcd for C28H37Ge2NNaO2+: 590.1140 (M + Na)+, found: 590.1143. Procedure for the Preparation of 6c. A dried 10 mL Schlenk tube was charged with 1-fluoro-2-iodobenzene 1a (22.3 mg, 0.10 mmol, 1.0equiv), 1,1,1,2,2,2-hexamethyldigermane 2b (35.3 mg, 0.15 mmol, 1.5 equiv), 1,4-epoxy-1,4dihydronaphthalene 3l (28.8 mg, 0.20 mmol, 2 equiv), Pd(OAc)2 (2.3 mg, 0.01 mmol, 10mol%), triphenylphosphine (PPh3) (5.3 mg, 0.02 mmol, 20 mol%), Cs2CO3 (66 mg, 0.20 mmol, 2.0equiv), and DMF (1.0 mL) and then the tube was evacuated and back filled with nitrogen (10 times). After stirring at 100 ℃for 12 h, After cooling to room temperature, the reaction mixture was diluted with ethyl acetate (15 mL), washed with H2O (10 ml, 3 times), dried over Na2SO4 and concentrated in vacuo. The residue was purified by preparative thin layer chromatography (PTLC) with ethyl acetate: hexane = 1: 10 to give the corresponding products trimethyl(1-(3(trimethylgermyl)-1,2,3,4-tetrahydro-1,4-epoxynaphthalen-2yl)naphthalen-2-yl)germane (6c) (35.9 mg, 71%) as white solid, mp 105-106 ℃. 1H NMR (500 MHz, CDCl3) δ 9.16 – 9.11 (m, 1H), 7.84 – 7.80 (m, 1H), 7.72 (d, J = 8.2 Hz, 1H), 7.52 – 7.46 (m, 3H), 7.29 (d, J = 7.0 Hz, 1H), 7.27 – 7.16 (m, 3H), 5.79 (s, 1H), 5.56 (s, 1H), 3.79 (d, J = 10.4 Hz, 1H), 1.64 (d, J = 10.4 Hz, 1H), 0.23 (s, 9H), -0.33 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 147.1, 146.2, 143.7, 142.3, 134.7, 132.2, 130.1, 128.4, 127.4, 126.9, 126.73 (s), 126.3, 125.8, 125.7, 118.5, 118.1, 83.4, 82.4, 53.5, 38.3, 0.7, -1.3; HRMS (ESITOF) m/z: calcd for C26H32Ge2NaO+: 531.0769 (M + Na)+, found: 531.0770. (3-Fluoro-2-(3-(trimethylgermyl)-1,2,3,4-tetrahydro-1,4epoxynaphthalen-2-yl)phenyl)trimethylgermane (6d) (33.6 mg, 71%). Colorless oil. 1H NMR (500 MHz, CDCl3) δ 7.25 – 7.22 (m, 2H), 7.22 – 7.19 (m, 1H), 7.19 – 7.13 (m, 3H), 7.07 – 7.02 (m, 1H), 5.59 (d, J = 2.4 Hz, 1H), 5.39 (s, 1H), 3.21 (d, J = 9.9 Hz, 1H), 1.49 (d, J = 9.9 Hz, 1H), 0.23 (s, 9H), -0.09 (d, J = 0.8 Hz, 9H); 13C NMR (126 MHz, CDCl3) δ 161.0 (d, J = 252.9 Hz), 146.7 (d, J = 81.7 Hz), 146.4, 133.3 (d, J = 11.9 Hz), 129.2 (d, J = 3.2 Hz), 127.9 (d, J = 7.4 Hz), 126.6, 126.2, 118.4, 117.9, 117.5, 117.3, 83.3 (d, J = 2.7 Hz), 81.6, 49.1(d, J = 3.2 Hz), 38.6, 0.3, -1.9.(d, J = 2.4 Hz); HRMS (ESI-TOF) m/z: calcd for C22H29FGe2NaO+: 499.0518 (M + Na)+, found: 499.0520. (3-Chloro-2-(3-(trimethylgermyl)-1,2,3,4-tetrahydro-1,4epoxynaphthalen-2-yl)phenyl)trimethylgermane (6e) (35.3mg, 72%). White solid, mp 78-79 ℃. 1H NMR (500 MHz, CDCl3) δ 7.36 (dd, J = 7.9, 1.3 Hz, 1H), 7.28 (dd, J = 7.3, 1.4 Hz, 1H), 7.23 (d, J = 7.1 Hz, 2H), 7.20 – 7.12 (m, 3H), 5.94 (s, 1H), 5.38 (s, 1H), 3.44 (d, J = 10.2 Hz, 1H), 1.51 (d, J = 10.2 Hz, 1H), 0.17 (s, 9H), -0.07 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 147.5, 147.1, 146.4, 143.0, 133.2, 132.7, 132.3, 127.5, 126.6, 126.2, 118.5, 117.9, 81.5, 81.4, 52.4, 38.6, 0.7, -1.4; HRMS (ESI-TOF) m/z: calcd for C22H29ClGe2NaO+: 515.0223 (M + Na)+, found: 515.0225. Trimethyl(3-methyl-2-(3-(trimethylgermyl)-1,2,3,4tetrahydro-1,4-epoxynaphthalen-2-yl)phenyl)germane (6f) (28.7 mg, 61%). White solid, mp 97-98 ℃. 1H NMR (500 MHz, CDCl3) δ 7.25 – 7.21 (m, 3H), 7.20 – 7.14 (m, 3H), 7.12 (t, J = 7.3 Hz, 1H), 5.66 (s, 1H), 5.38 (s, 1H), 3.47 (d, J = 10.3 Hz, 1H), 2.65 (s, 3H), 1.55 (d, J = 10.3 Hz, 1H), 0.16 (s, 9H), 0.14 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 146.7, 146.3, 144.9, 144.1, 136.5, 133.6, 131.7, 126.6, 126.3, 126.2, 118.4, 118.0, 81.9, 81.2, 52.4, 39.0, 21.8, 0.8, -1.5; HRMS (ESI-TOF)



m/z: calcd for C23H32Ge2NaO+: 495.0769 (M + Na)+, found: 495.0770. (3-Methoxy-2-(3-(trimethylgermyl)-1,2,3,4-tetrahydro-1,4epoxynaphthalen-2-yl)phenyl)trimethylgermane (6g) (40.3 mg, 83%). Colorless oil. 1H NMR (500 MHz, CDCl3) δ 7.23 – 7.19 (m, 2H), 7.18 (d, J = 7.3 Hz, 1H), 7.16 – 7.10 (m, 2H), 6.98 (dd, J = 7.4, 1.1 Hz, 1H), 6.86 (d, J = 8.1 Hz, 1H), 5.64 (s, 1H), 5.35 (s, 1H), 3.79 (s, 3H), 3.23 (d, J = 10.0 Hz, 1H), 1.44 (d, J = 10.0 Hz, 1H), 0.17 (s, 9H), -0.13 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 158.0, 148.0, 146.4, 145.4, 133.7, 127.3, 126.2, 126.0, 125.6, 118.4, 117.6, 111.4, 82.8, 81.4, 54.3, 50.6, 37.9, 0.5, -1.8; HRMS (ESI-TOF) m/z: calcd for C23H32Ge2NaO2+: 511.0718 (M + Na)+, found: 511.0718. Methyl 3-methyl-5-(trimethylgermyl)-4-(3(trimethylgermyl)-1,2,3,4-tetrahydro-1,4-epoxynaphthalen-2yl)benzoate (6h) (32.2 mg, 61%). White solid, mp 154-155 ℃. 1 H NMR (500 MHz, CDCl3) δ 7.88 (d, J = 1.0 Hz, 1H), 7.83 (s, 1H), 7.26 – 7.23 (m, 2H), 7.21 – 7.15 (m, 2H), 5.66 (s, 1H), 5.39 (s, 1H), 3.90 (s, 3H), 3.51 (d, J = 10.3 Hz, 1H), 2.70 (s, 3H), 1.57 (d, J = 10.3 Hz, 1H), 0.19 (s, 9H), -0.14 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 167.4, 149.9, 146.3, 146.2, 145.7, 136.7, 134.6, 132.4, 127.5, 126.8, 126.4, 118.4, 118.0, 81.6, 81.2, 52.7, 52.0, 39.2, 21.8, 0.7, -1.4; HRMS (ESI-TOF) m/z: calcd for C25H34Ge2NaO3+: 553.0824 (M + Na)+, found: 553.0825. (5-Methoxy-2-(3-(trimethylgermyl)-1,2,3,4-tetrahydro-1,4epoxynaphthalen-2-yl)phenyl)trimethylgermane (6i) (34.0 mg, 70%). White solid, mp 100-102 ℃. 1H NMR (500 MHz, CDCl3) δ 7.63 – 7.59 (m, 1H), 7.26 – 7.22 (m, 2H), 7.20 – 7.13 (m, 2H), 6.91 – 6.88 (m, 2H), 5.34 (s, 1H), 5.28 (s, 1H), 3.81 (s, 3H), 3.08 (d, J = 9.3 Hz, 1H), 1.49 (d, J = 9.3 Hz, 1H), 0.28 (s, 9H), -0.10 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 157.6, 147.6, 145.6, 142.8, 141.4, 128.8, 126.6, 126.2, 118.7, 118.6, 118.0, 113.9, 86.9, 81.2, 55.2, 48.0, 40.0, -0.1, -1.5; HRMS (ESI-TOF) m/z: calcd for C23H32Ge2NaO2+: 511.0718 (M + Na)+, found: 511.0719. Trimethyl(2-(3-(trimethylgermyl)-1,2,3,4-tetrahydro-1,4epoxynaphthalen-2-yl)thiophen-3-yl)germane (6j) (24.6 mg, 53%). Light yellow oil. 1H NMR (500 MHz, CDCl3) δ 7.21 – 7.15 (m, 3H), 7.15 – 7.08 (m, 2H), 6.83 (d, J = 5.0 Hz, 1H), 5.27 (s, 1H), 5.24 (s, 1H), 3.42 (d, J = 9.2 Hz, 1H), 1.41 (d, J = 9.2 Hz, 1H), 0.25 (s, 9H), -0.07 (s, 9H).13C NMR (126 MHz, CDCl3) δ 152.3, 147.4, 144.6, 137.7, 130.5, 126.9, 126.4, 124.0, 119.0, 117.8, 86.9, 81.7, 45.6, 39.2, -0.2, -1.6; HRMS (ESI-TOF) m/z: calcd for C20H28Ge2NaOS+: 487.0177 (M + Na)+, found: 487.0178. Procedure for the Gram-Scale Alkylation of 4l. A 150 mL dried Schlenk tube was charged with 1-iodonaphthalene 1a (1.27 g, 5 mmol), hexamethyldisilane 2a (1.10 g, 7.5 mmol, 1.5 equiv), 1,4-epoxy-1,4-dihydronaphthalene 3l (1.43 g, 10 mmol, 2 equiv), Pd(OAc)2 (0.115 g, 0.5 mmol, 10 mol %), PPh3 (0.265 g, 1 mmol, 20 mol %), Cs2CO3 (3.26 g, 10 mmol, 2 equiv), and DMF (50 mL) and then the tube was evacuated and back filled with nitrogen (10 times). The reaction mixture was heated to 100 °C for 24 hours under vigorous stirring. Upon completion, the reaction mixture was cooled to room temperature, diluted with ethyl acetate, and filtered through a pad of celite. The filtrate was concentrated under vacuum, and the resulting residue was purified by column chromatography with ethyl acetate : hexane = 1 : 100 to give the corresponding products 4l (1.88 g, 87%) as a white solid.

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Synthesis of 7a. A dried 10 mL Schlenk tube was charged with 4a (37 mg, 0.1 mmol) and N-iodosuccinimide (67.5 mg, 3 equiv.). The test tube was evacuated and back-filled with dry nitrogen (this sequence was repeated three times). Dry acetonitrile (1.5 mL) was then added into the tube by syringe through the septum under a positive pressure of nitrogen and the resulting mixture was stirred at room temperature for 12 h. Then the mixture was concentrated and purified by column chromatography in silica gel (hexanes) to yield the title product (3-(2-iodonaphthalen-1-yl)bicyclo[2.2.1]heptan-2yl)trimethylsilane (7a) (41.2 mg, 98%) as white solid, mp 9596 ℃. 1H NMR (500 MHz, CDCl3) δ 8.63 – 8.59 (m, 1H), 7.91 (d, J = 8.6 Hz, 1H), 7.80 – 7.76 (m, 1H), 7.47 – 7.44 (m, 2H), 7.32 (d, J = 8.6Hz, 1H), 3.95 (d, J = 11.1 Hz, 1H), 3.06 (d, J = 2.2 Hz, 1H), 2.49 (d, J = 4.1 Hz, 1H), 2.24 (d, J = 9.7 Hz, 1H), 1.92 – 1.86 (m, 2H), 1.69 – 1.61 (m, 2H), 1.56 – 1.51 (m, 2H), -0.52 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 143.3, 137.2, 134.4, 131.9, 129.0, 128.1, 126.0, 125.7, 125.3, 106.5, 59.7, 42.6, 40.9, 40.5, 39.1, 34.6, 32.2, -0.6; HRMS (ESI-TOF) m/z: calcd for C20H25INaSi+: 443.0662 (M + Na)+, found: 443.0660. Synthesis of 7b. A dried 10 mL Schlenk tube was charged with 4l (42 mg, 0.1 mmol) and N-iodosuccinimide (67.5 mg, 3 equiv.). The test tube was evacuated and back-filled with dry nitrogen (this sequence was repeated three times). Dry acetonitrile (1.5 mL) was then added into the tube by syringe through the septum under a positive pressure of nitrogen and the resulting mixture was stirred at room temperature for 12 h. Then the mixture was concentrated and purified by column chromatography in silica gel (Hexanes) to yield the title product (3-(2-iodonaphthalen-1-yl)-1,2,3,4-tetrahydro-1,4epoxynaphthalen-2-yl)trimethylsilane (7b) (45 mg, 96%) as white solid, mp 169-171℃. 1H NMR (500 MHz, CDCl3) δ 9.10 – 9.06 (m, 1H), 7.89 (d, J = 8.6 Hz, 1H), 7.83 – 7.80 (m, 1H), 7.55 – 7.49 (m, 2H), 7.40 (d, J = 8.6 Hz, 1H), 7.29 (d, J = 7.1 Hz, 1H), 7.26 (d, J = 7.4 Hz, 1H), 7.25 – 7.16 (m, 2H), 5.90 (s, 1H), 5.59 (s, 1H), 4.02 (d, J = 10.6 Hz, 1H), 1.79 (d, J = 10.6 Hz, 1H), -0.30 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 146.8, 146.7, 141.0, 136.6, 134.2, 132.1, 128.9, 128.7, 127.2, 126.8, 126.5, 126.2, 126.2, 118.3, 118.2, 106.3, 83.0, 81.6, 58.6, 34.3, -1.0; HRMS (ESI-TOF) m/z: calcd for C23H23INaOSi+: 493.0455 (M + Na)+, found: 493.0457. Procedure for the Preparation of 8. A dried 10 mL Schlenk tube was charged with 7b (94 mg, 0.2 mmol), hexamethyldisilane 2a (44 mg, 0.3 mmol, 1.5 equiv), Pd(OAc)2 (4.6 mg, 0.02 mmol, 10 mol%), PPh3 (10.8 mg, 0.04 mmol, 20 mol%), 1,4-epoxy-1,4-dihydronaphthalene 3l (57 mg, 0.4 mmol, 2 equiv), Cs2CO3 (132 mg, 0.4 mmol, 2 equiv), and DMF (2 mL) and then the tube was evacuated and back filled with nitrogen (10 times). The reaction mixture was heated to 60 °C for 24 hours under vigorous stirring. Upon completion, the reaction mixture was cooled to room temperature, diluted with ethyl acetate, and filtered through a pad of celite. The filtrate was concentrated under vacuum, and the resulting residue was purified by preparative thin layer chromatography (PTLC) with ethyl acetate: hexane = 1: 100 gives three isomers of corresponding products trimethyl(3-(3-(trimethylsilyl)-1,2,3,4tetrahydro-1,4-epoxynaphthalen-2-yl)-4-(3-(trimethylsilyl)1,2,3,4-tetrahydro-1,4-epoxynaphthalen-2-yl)naphthalen-2yl)silane (8) in a ratio of 1:2:1 (8-1: 8-2: 8-3) (78 mg, 62%) as white solid. 8-1: White solid, mp 256-258 ℃. 1H NMR (500 MHz, CDCl3) δ 8.96 (d, J = 8.4 Hz, 1H), 8.30 (s, 1H), 7.79 (dd, J =


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8.0, 1.3 Hz, 1H), 7.48 – 7.41 (m, 2H), 7.21 – 7.18 (m, 1H), 7.13 – 7.06 (m, 7H), 6.01 (s, 1H), 5.88 (s, 1H), 5.47 (s, 1H), 5.25 (s, 1H), 3.57 (d, J = 10.4 Hz, 1H), 3.48 (d, J = 9.6 Hz, 1H), 1.05 (d, J = 10.4 Hz, 1H), 0.92 (d, J = 9.7 Hz, 1H), 0.53 (s, 9H), -0.27 (s, 9H), -0.34 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 147.2, 146.94, 146.87, 146.85, 144.7, 139.5, 137.6, 135.5, 132.1, 132.1, 128.9, 127.0, 126.6, 126.5, 126.13, 126.09, 126.0, 125.0, 118.5, 118.4, 117.8, 117.6, 83.1, 81.6, 80.24, 80.20, 50.1, 48.5, 36.0, 34.0, 4.9, -0.7, -0.8; HRMS (ESI-TOF) m/z: calcd for C39H48NaO2Si3+: 655.2854 (M + Na)+, found: 655.2852. 8-2: White solid, mp 231-232 ℃. 1H NMR (500 MHz, CDCl3) δ 8.36 (s, 1H), 7.72 (dd, J = 7.9, 1.5 Hz, 1H), 7.65 (d, J = 8.6 Hz, 1H), 7.39 – 7.30 (m, 3H), 7.20 – 7.17 (m, 3H), 7.17 – 7.09 (m, 4H), 6.12 (s, 1H), 5.76 (s, 1H), 5.40 (s, 1H), 5.32 (s, 1H), 4.63 (d, J = 9.9 Hz, 1H), 4.30 (d, J = 10.4 Hz, 1H), 1.66 (d, J = 10.4 Hz, 1H), 1.58 (d, J = 9.9 Hz, 1H), 0.53 (s, 9H), -0.28 (s, 9H), -0.47 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 150.3, 147.4, 146.6, 144.6, 143.3, 140.7, 137.6, 135.6, 134.7, 131.5, 129.3, 127.0, 126.7, 126.7, 126.1, 126.1, 124.8, 124.0, 120.3, 118.5, 117.9, 116.7, 82.7, 81.6, 80.4, 80.1, 47.5, 44.6, 42.8, 38.0, 6.6, -0.1, -1.5; HRMS (ESI-TOF) m/z: calcd for C39H48NaO2Si3+: 655.2854 (M + Na)+, found: 655.2855. 8-3: White solid, mp 298-300 ℃. 1H NMR (500 MHz, CDCl3) δ 9.34 (d, J = 8.8 Hz, 1H), 7.88 (s, 1H), 7.76 (dd, J = 8.0, 1.4 Hz, 1H), 7.52 – 7.48 (m, 1H), 7.47 – 7.42 (m, 1H), 7.41 – 7.37 (m, 1H), 7.23 – 7.20 (m, 2H), 7.16 – 7.12 (m, 2H), 7.12 – 7.07 (m, 3H), 6.15 (s, 1H), 5.63 (s, 1H), 5.49 (s, 1H), 5.15 (s, 1H), 4.87 (d, J = 10.6 Hz, 1H), 3.66 (d, J = 10.8 Hz, 1H), 1.69 (d, J = 10.6 Hz, 1H), 1.38 (d, J = 10.8 Hz, 1H), 0.08 (s, 9H), -0.31 (s, 9H), -0.41 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 148.3, 147.7, 146.1, 145.3, 144.3, 141.8, 136.7, 136.0, 134.1, 133.2, 128.7, 127.9, 126.8, 126.5, 126.2, 126.0, 125.6, 125.1, 119.8, 118.4, 117.7, 117.5, 83.7, 82.1, 81.2, 80.0, 54.0, 45.0, 39.9, 39.1, 1.5, -0.6, -0.8; HRMS (ESI-TOF) m/z: calcd for C39H48NaO2Si3+: 655.2854 (M + Na)+, found: 655.2855. Procedure for the Preparation of 9. A 10 mL tube was charged with 7b (47 mg, 0.1 mmol), MeOH (1 mL), and concentrated HCl (0.1 mL, 12 equiv). The reaction mixture was heated to 70 °C for 12 hours under vigorous stirring. Upon completion, the reaction mixture was cooled to room temperature, the reaction misture was concentrated under vacuum, and the resulting residue was purified by preparative thin layer chromatography (PTLC) with ethyl acetate: hexane = 1: 100 give the corresponding products 2-iodo-1,2'-binaphthalene (9) (38.0, 99%) as white solid, mp 89-90 ℃. 1H NMR (500 MHz, CDCl3) δ 8.06 – 8.02 (m, 2H), 8.02 – 7.98 (m, 1H), 7.95 – 7.88 (m, 2H), 7.79 (s, 1H), 7.64 (d, J = 8.7 Hz, 1H), 7.62 – 7.56 (m, 2H), 7.55 – 7.50 (m, 1H), 7.45 (d, J = 8.4 Hz, 1H), 7.42 (dd, J = 8.3, 1.7 Hz, 1H), 7.32 – 7.37 (m, 1H); 13C NMR (126 MHz, CDCl3) δ 144.3, 140.6, 135.5, 133.5, 133.5, 132.8, 132.8, 129.1, 129.0, 128.2, 128.1, 128.1, 127.9, 127.9, 127.2, 126.8, 126.3, 126.2, 98. 5; HRMS (ESI-TOF) m/z: calcd for C20H14I+: 381.0135 (M + H)+, found: 381.0135.

ASSOCIATED CONTENT Supporting Information. The Supporting Information is available free of charge on the ACS Publications website.

1 H and 13C NMR spectra of new compounds, and X-ray data for 4l (CCDC 1838284) and 5i (CCDC 1838283)

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

Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT This work was supported by the NSF of China (21672075) and the Program for New Century Excellent Talents in Fujian Province University.

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Palladium-Catalyzed Catellani-Type bis-Silylation and bis

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