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Article Cite This: J. Org. Chem. 2018, 83, 862−870

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Broad Synthesis of Disubstituted Dihydrofuran-Fused [60]Fullerene Derivatives via Cu(I)/Ag(I)-Mediated Synergistic Annulation Reaction Shilu Xia, Tong-Xin Liu,* Pengling Zhang, Jinliang Ma, Qingfeng Liu, Nana Ma, Zhiguo Zhang, and Guisheng Zhang* Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, Henan Key Laboratory of Organic Functional Molecule and Drug Innovation, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007, P. R. China S Supporting Information *

ABSTRACT: A novel and efficient Cu(I)/Ag(I)-mediated synergistic annulation reaction of [60]fullerene with diarylethanones, benzoylacetonitriles, and β-dicarbonyl compounds has been developed for the direct construction of diverse disubstituted dihydrofuran-fused [60]fullerene derivatives. This transformation exhibits a remarkably broad substrate scope and functional group tolerance and provides a useful method to a scarce class of fullerene derivatives.

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INTRODUCTION The abundant availability of organofullerenes in materials science, electronic devices, and biomedicine1 has made functionalization of fullerenes attract great attention, and numerous fullerene derivatives with fused different organic functional units have been prepared.2,3 As a useful basic unit, furan has recently drawn growing attention in the organic optoelectronic area, especially for the fusion of furan rings to an all-carbon aromatic system.4 Different from other all-carbon aromatic systems, fullerenes are a class of unique three-dimensional electron-deficient allcarbon aromatic structures,5 and thus the furan-fused fullerene derivatives might exhibit the different chemical/physical properties leading to new applications in related fields. However, the furan-fused fullerene derivatives have been rarely seen in the literature of organic electronic research, probably because of the lack of the corresponding available fullerene adducts. To date, the reported routes to these compounds are fairly limited, which include base-promoted nucleophilic addition of C60 with β-dicarbonyl compounds,6 Mn(III)and/or Cu(II)-mediated radical cycloaddition of C60 with βdicarbonyl compounds or aromatic methyl ketones,7 palladiumcatalyzed C−H activation of C60 with phenols,8 and indirect transformation from [60]fullerene-fused lactones.9 Despite these advances, most of the cases still suffer from the limitation of a narrow scope of substrates and low yields,6,7,9 which hinders their wide applications in related fields. Therefore, the development of efficient methods with a broad substrate scope for the diverse synthesis of furan-fused fullerene derivatives is highly demanding. Recently, we successfully achieved the synthesis of a series of different types of fullerene-fused cyclic derivatives,10 including Cu(OAc)2-medaited N-heteroannulation reaction of C60 with N-sulfonylated o-amino-aromatic methyl ketones and O-alkyl oximes for the construction of the © 2017 American Chemical Society

scarce C60-fused tetrahydroazepinones and tetrahydroazepinonimines.10a As a continuation, we herein describe a Cu(I)/ Ag(I)-mediated synergistic O-heteroannulation reaction of [60]fullerene with diarylethanones, benzoylacetonitriles, and β-dicarbonyl compounds for the preparation of diverse disubstituted dihydrofuran-fused [60]fullerene derivatives. Notably, this reaction exhibits a wide range of substrate scope and functional group compatibility, which provides new possibilities for certain kinds of optoelectronic applications.

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RESULTS AND DISCUSSION We began our optimization studies with 2-(4-nitrophenyl)-1phenylethan-1-one 1a as a model substrate (Table 1). The initial use of O2 as the oxidant and CuI as the catalyst failed to provide any of the desired product (Table 1, entry 1). Subsequently, other oxidizing reagents, including K2S2O8, Oxone, PhI(OAc)2, and Ag2O, were screened. To our delight, the reaction that employed Ag2O as an oxidant afforded the desired product 2a in 48% yield, while other oxidants proved to be ineffective (Table 1, entries 2−5). A further examination of Ag2CO3 and AgOAc indicated that Ag2O was the most effective oxidant for this transformation (Table 1, entry 5 vs entries 6 and 7). Replacing CuI with other Cu(I) catalysts such as CuCl, CuBr, CuBr·SMe2, Cu(CH3CN)4PF6, and CuTc (copper(I) thiophene-2-carboxylate) all showed poor performance in the reaction (Table 1, entries 8−12). Prolonging or shortening the reaction time did not result in higher yields (Table 1, entries 13 and 14). The control experiment revealed that the reaction could also furnish the corresponding derivative 2a in the absence of CuI, but only in 8% yield, clearly indicating the key role of the Cu(I) catalyst in the present transformation (Table Received: November 9, 2017 Published: December 8, 2017 862

DOI: 10.1021/acs.joc.7b02848 J. Org. Chem. 2018, 83, 862−870

Article

The Journal of Organic Chemistry Table 1. Optimization of the Reaction Conditionsa

entry

catalyst Cu(I/II)

oxidant

time (h)

yield (%)b

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

CuI CuI CuI CuI CuI CuI CuI CuCl CuBr CuBr·SMe2 Cu(CH3CN)4PF6 CuTc CuI CuI

O2 K2S2O8 Oxone PhI(OAc)2 Ag2O Ag2CO3 AgOAc Ag2O Ag2O Ag2O Ag2O Ag2O Ag2O Ag2O Ag2O Ag2O Ag2O Ag2O

7 7 7 7 7 7 7 7 7 7 7 7 5 9 7 7 7 7 7 7

no reaction no reaction trace no reaction 48 (85) 32 (57) 26 (71) 28 (48) 31 (53) 36 (69) 32 (86) 39 (76) 35 (66) 36 (62) 8 (68) 28 (39) 44 (50) 39 (57) 4 (14) no reaction

Cu(OAc)2 CuCl2 CuBr2 CuCl2 CuBr2

a

Unless otherwise specified, all reactions were carried out with C60 (0.075 mmol), 1a (0.15 mmol), Cu(I/II) (0.015 mmol), and an oxidant (0.15 mmol) in ODCB (5 mL)/TFA (0.2 mL) at 120 °C in air for the designated time. bIsolated yield. Those in parentheses were based on consumed C60.

carbazole motifs were also compatible with the reaction, demonstrating a great potential for the application of this method in materials science. Besides diarylethanones, 1phenylpropan-2-one 1l was found to be a suitable substrate, and the corresponding derivative 2l was obtained in a moderate yield. Unfortunately, the reaction did not proceed when acetophenone was employed as a substrate. To further explore the scope of the reaction, a wide array of 3-oxopropanenitrile compounds, including different substituted benzoylacetonitriles 1m−1q, 3-oxo-3-(thiophen-2-yl)propanenitrile 1r, 3-(furan-2-yl)-3-oxopropanenitrile 1s, and 3-oxobutanenitrile 1t, were also evaluated. Gratifyingly, they all underwent an efficient O-heteroannulation reaction with [60]fullerene to afford another novel type of disubstituted dihydrofuran derivatives with cyano moiety 2m−2t in 28%− 48% yields under the optimized conditions. Moreover, various functional groups, such as methoxy, fluorine, bromine, and ester groups, were also well-tolerated. The presence of the unique and versatile reactivity of the cyano functional group, especially, provides an important and convenient handle for further modification of the corresponding products.11 In addition, an attempt using methyl cyanoacetate 1u as a substrate for the synthesis of derivative 2u switched to afford methanofullerene derivative 3u in 29% yield, which might be attributed to the difficulty in the formation of an enolate intermediate. Finally, the reaction system was further expanded to βdicarbonyl compounds. As expected, β-ketoesters 1v and 1w

1, entry 15). In addition, the combination of different Cu(II) catalysts with Ag2O could also accomplish this transformation (Table 1, entries 16−18); however, no or trace target product was obtained in the absence of Ag2O (Table 1, entries 19 and 20). It should be noted that the reaction did not proceed without TFA. Thus, the molar ratio of 1:2:0.2:2 for the reagents C60, 1a, CuI, and Ag2O and the reaction temperature of 120 °C in ODCB/TFA were chosen as the optimized reaction conditions. With the optimized system in hand, we next explored the scope and generality of the transformation. A variety of diarylethanone compounds were first investigated, as shown in Scheme 1. The electronic effect of the substituent group on both phenyl rings has an obvious influence on the reaction. Generally, the substrates bearing an electron-withdrawing group (1a, 1d, and 1g) show a higher reactivity than those with an electron-donating group (1c, 1e, and 1f), affording the corresponding dihydrofuran-fused [60]fullerene derivatives (2a, 2d, and 2g) in higher yields. Furthermore, the electronic effect on the phenyl ring adjacent to CO is more sensitive than that of the other phenyl ring. For example, the presence of the strong electron-donating group (OMe) at the p-position on the corresponding phenyl ring failed in delivering the desired adduct 2c. Satisfyingly, the bromide and sulfonamide groups were tolerated, thus offering the possibility of further derivatization of the product 2h. It should be mentioned that the substrates 1i, 1j, and 1k with fluorene, dibenzofuran, and 863

DOI: 10.1021/acs.joc.7b02848 J. Org. Chem. 2018, 83, 862−870

Article

The Journal of Organic Chemistry Scheme 1. Scope of the Annulation Reactiona,b

864

DOI: 10.1021/acs.joc.7b02848 J. Org. Chem. 2018, 83, 862−870

Article

The Journal of Organic Chemistry Scheme 1. continued

a Unless otherwise specified, all reactions were carried out with C60 (0.075 mmol), 1a (0.15 mmol), CuI (0.015 mmol), and Ag2O (0.15 mmol) in ODCB (5 mL)/TFA (0.2 mL) at 120 °C in air for 7 h. bIsolated yield. c9 h. d4 equiv of 1i was used, 130 °C, 16 h. e3 h. f4 equiv of 1w was used, 130 °C, 18 h. g4 equiv of 1x was used, 4 h. hThe reaction was carried out with C60 (0.075 mmol), 1a (0.15 mmol), and CuCl (0.0375 mmol) in ODCB (5 mL)/TFA (0.2 mL)/CH3CN (1 mL) at 120 °C for 12 h.

and β-diketones 1x and 1y all smoothly proceeded in this transformation to produce the desired products 2v−2y in comparable yields with those reported in the literature.6,7 Interestingly, for the reaction of [60]fullerene with 1,3indanedione 1z, the methanofullerene derivative 3z was selectively obtained in 37% yield instead of the dihydrofuran adduct 2z, although the exact reason is not clear. More importantly, the substrates 1,3-diphenylpropane-1,3-dione 1aa and 3-oxo-3-phenylpropanamides 1bb−1dd could also success-

fully react as anticipated giving the corresponding products 2aa−2dd under optimized and appropriately adjusted reaction conditions, respectively. After proving a wide substrate scope tolerance, we turned to investigate the reaction mechanism. A series of control experiments were carried out, as illustrated in Scheme 2. With the treatment of C60 with 4-hydroxycoumarin 1ee under the optimized conditions, the dihydrofuran derivative 2ee was obtained in 41% yield, revealing that the current transformation 865

DOI: 10.1021/acs.joc.7b02848 J. Org. Chem. 2018, 83, 862−870

Article

The Journal of Organic Chemistry Scheme 2. Probe Reaction Mechanism

Scheme 3. Proposed Reaction Mechanism

hexadiene-1-ylidene)-p-tolyloxy) could obviously retard or even completely suppress the reaction, which indicated that the current transformation might involve a free radical pathway (Scheme 2b), although an attempt on obtaining the possible radical intermediate formed in the reaction failed. Although the mechanism of this transformation is not completely clear yet, on the basis of the above results, a possible mechanism to rationalize the formation of dihydrofuran-fused [60]fullerene derivatives 2 is presented in Scheme 3. With the assistance of Cu(I) and TFA, the equilibrium between the substrate 1 and enolate intermediate I is favorable for the enolate I. Subsequently, a single electron transfer (SET)

more likely underwent an enolization process (Scheme 2a (i)). However, the product 2ee still could be isolated in a comparable yield in the absence of CuI and/or CF3COOH (Scheme 2a (ii−iv)), but no products were detected without Ag2O (Scheme 2a (v and vi)). These results and aforementioned optimization experiments demonstrated that the combination of a Cu salt and TFA is crucial for the formation of an enolate intermediate, while the Ag salt is primarily responsible for the conversion from enolate intermediate to final product. Additionally, the addition of the free radical scavengers 2,2,6,6-tetramethylpiperidine-1-oxy (TEMPO) and galvinoxyl (2,6-di-tert-butyl-α-(3,5-di-tert-butyl-4-oxo-2,5 cyclo866

DOI: 10.1021/acs.joc.7b02848 J. Org. Chem. 2018, 83, 862−870

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The Journal of Organic Chemistry

mmol). After dissolving the solids in a mixture of anhydrous odichlorobenzene (5 mL) and trifluoroacetic acid (0.2 mL) by sonication, the sealed mixture was heated with stirring in an oil bath preset at the designated reaction temperature (120 or 130 °C) for the desired time (monitored by TLC). The reaction mixture was filtered through a silica gel plug to remove any insoluble material. After the solvent was evaporated in vacuo, the residue was separated on a silica gel column with CS2 as the eluent to recover unreacted C60, and then the eluent was switched to CS2/CH2Cl2 (10:1 v/v) [for 2b with CS2; 2h and 2q with CS2/CH2Cl2 (5:1 v/v)] to give products 2a−2aa, 3u, and 3z. Procedure for the Synthesis of Products 2bb−2dd. A dry 15 mL tube equipped with a magnetic stir bar was charged with C60 (54.0 mg, 0.075 mmol), 1bb−1dd (0.15 mmol), and CuCl (3.7 mg, 0.0375 mmol). After dissolving the solids in a mixture of anhydrous odichlorobenzene (5 mL), trifluoroacetic acid (0.2 mL), and acetonitrile (1 mL) by sonication, the sealed mixture was heated with stirring in an oil bath at 120 °C for 12 h (monitored by TLC). The reaction mixture was filtered through a silica gel plug to remove any insoluble material. After the solvent was evaporated in vacuo, the residue was separated on a silica gel column with CS2 as the eluent to recover unreacted C60, and then the eluent was switched to CS2/CH2Cl2 (5:1 v/v) to give products 2bb−2dd. Compound 2a: yield 34.2 mg, 48%; brown solid; mp >300 °C; 1H NMR (600 MHz, CDCl3/CS2) δ 8.29 (d, J = 8.4 Hz, 2H), 7.87 (d, J = 8.4 Hz, 2H), 7.74 (d, J = 7.2 Hz, 2H), 7.45 (t, J = 7.2 Hz, 1H), 7.41 (t, J = 7.2 Hz, 2H); 13C{1H} NMR (150 MHz, CDCl3/CS2 with Cr(acac)3 as a relaxation reagent, all 2C unless indicated) δ 152.6 (1C), 148.1 (1C), 148.0, 147.6 (1C), 147.4 (1C), 146.36, 146.3, 146.2, 146.1, 146.0, 145.6, 145.4, 145.3, 145.2, 145.1, 144.94, 144.91, 144.4, 144.3, 142.9, 142.8, 142.7, 142.6, 142.4, 142.3, 142.1, 141.8, 141.6, 140.9 (1C), 140.3, 140.0, 137.2, 136.2, 132.0, 130.1 (1C), 129.1 (1C), 128.6, 128.3, 124.4, 110.6 (1C), 100.7 (1C), 77.6 (1C); FT-IR ν/cm−1 (KBr) 1594, 1512, 1444, 1427, 1343, 1096, 993, 851, 801, 767, 748, 690, 526; UV−vis (CHCl3) λmax/nm 256, 317, 687; MALDI-TOF MS m/z calcd for C74H9NO3 [M]+ 959.0577, found 959.0565. Compound 2b: yield 25.5 mg, 37%; brown solid; mp >300 °C; 1H NMR (600 MHz, CDCl3/CS2) δ 7.75−7.74 (m, 2H), 7.64−7.63 (m, 2H), 7.46−7.43 (m, 2H), 7.41−7.35 (m, 4H); 13C{1H} NMR (150 MHz, CDCl3/CS2 with Cr(acac)3 as a relaxation reagent, all 2C unless indicated) δ 150.2 (1C), 148.6, 147.7 (1C), 147.0 (1C), 146.0, 145.9, 145.8, 145.62, 145.58, 145.5, 145.3, 145.2, 145.0, 144.8, 144.77, 144.7, 144.05, 144.02, 142.5, 142.4, 142.3, 142.0, 141.96, 141.8, 141.6, 141.3, 139.9, 139.5, 137.0, 135.6, 133.1 (1C), 130.8, 129.5 (1C), 129.0, 128.98, 128.1, 128.0, 127.7, 112.1 (1C), 99.6 (1C), 78.2 (1C); FT-IR ν/cm−1 (KBr) 1645, 1453, 1427, 1024, 746, 697, 526; UV−vis (CHCl3) λmax/nm 258, 318, 684; MALDI-TOF MS m/z calcd for C74H10O [M]+ 914.0726, found 914.0701. Compound 2d: yield 32.5 mg, 45%; brown solid; mp >300 °C; 1H NMR (600 MHz, CDCl3/CS2) δ 8.22 (d, J = 7.8 Hz, 2H), 7.94 (d, J = 7.8 Hz, 2H), 7.64 (t, J = 7.6 Hz, 2H), 7.52−7.45 (m, 3H); 13C{1H} NMR (150 MHz, CDCl3/CS2 with Cr(acac)3 as a relaxation reagent, all 2C unless indicated) δ 148.5 (1C), 148.02 (1C), 148.0, 147.6 (1C), 147.3 (1C), 146.3, 146.2, 146.1, 146.0, 145.9, 145.6, 145.5, 145.3, 145.1, 145.0, 144.8, 144.7, 144.3 (4C), 142.8, 142.7, 142.6, 142.5, 142.3, 142.2, 142.0, 141.8, 141.5, 140.2, 139.8, 137.2, 136.0, 135.9 (1C), 132.4 (1C), 130.7, 129.6, 129.0 (1C), 128.5, 123.4, 116.8 (1C), 100.1 (1C), 78.3 (1C); FT-IR ν/cm−1 (KBr) 1593, 1515, 1339, 1093, 990, 855, 746, 699, 562, 526; UV−vis (CHCl3) λmax/nm 258, 320, 687; MALDI-TOF MS m/z calcd for C74H9NO3 [M]+ 959.0577, found 959.0559. Compound 2e: yield 26.1 mg, 37%; brown solid; mp >300 °C; 1H NMR (600 MHz, CDCl3/CS2) δ 7.67 (d, J = 8.4 Hz, 2H), 7.63 (d, J = 7.2 Hz, 2H), 7.43 (t, J = 7.2 Hz, 2H), 7.39−7.36 (m, 1H), 6.86 (d, J = 8.4 Hz, 2H), 3.84 (s, 3H); 13C{1H} NMR (150 MHz, CDCl3/CS2 with Cr(acac)3 as a relaxation reagent, all 2C unless indicated) δ 159.9 (1C), 150.0 (1C), 148.8, 147.66 (1C), 146.9 (1C), 145.9, 145.8, 145.7, 145.6, 145.5, 145.46, 145.3, 145.27, 144.9, 144.8, 144.7, 144.6, 144.0, 143.96, 142.5, 142.3, 142.26 (4C), 142.0, 141.9, 141.7, 141.6, 141.2, 139.8, 139.4, 137.0, 135.5, 133.4 (1C), 130.9, 129.1, 128.9, 127.9 (1C),

process from I to oxidant occurs to produce the carbon centered radical II,7,12 which could be captured by C60 to produce fullerene radical III. As a key intermediate, radical III could further undergo enolization and SET process to generate biradical species IV, which then converts to the final product 2 via an intramolecular coupling. Another parallel reaction pathway involving the fullerenyl cation intermediate is also proposed according to previous reports.13 In our reaction conditions, radical III is further oxidized by Ag(I) to generate the fullerenyl cation V. After that, it undergoes a sequential enolization and nucleophilic addition to afford the derivative 2. The electrochemical properties of the selected representative products along with C60 have been investigated by cyclic voltammetry (CV), and their half-wave reduction potentials are summarized in Table 2. It was found that, whether redox Table 2. Half-Wave Reduction Potentials (V) of C60 and Representative Productsa compound

E1

E2

E3

C60 2a 2b 2d 2e 2m 2n 2q 2v 2x 2aa 2bb

−1.08 −1.10 −1.13 −1.10

−1.46

−1.93

−1.52

−1.98

−1.51 −1.06 −1.07 −1.06 −1.13 −1.14 −1.12 −1.11

−1.44 −1.45 −1.45

−1.83 −1.92 −1.80

a

Versus ferrocene/ferrocenium. Experimental conditions: 1 mM compound 2 and 0.1 M (n-Bu)4NClO4 in anhydrous o-dichlorobenzene. Reference electrode, SCE; working electrode, Pt; auxiliary electrode, Pt wire; scanning rate, 20 mV s−1.

processes of the compound are reversible or not, it obviously depends on the nature of the substituent. However, the first redox process of selected compounds was reversible (except for 2e) at a scanning rate of 20 mV s−1. Moreover, their E1 values were close to the pristine C60 because of the attached electronegative oxygen atoms. For 2e, the first redox processes are irreversible, indicating that it undergoes a chemical reaction process after receiving one electron.

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CONCLUSION In summary, we have developed an efficient method for the direct construction of a series of diverse disubstituted dihydrofuran-fused [60]fullerene derivatives via the Cu(I)/ Ag(I)-mediated synergistic annulation reaction of [60]fullerene with diarylethanones, benzoylacetonitriles, and β-dicarbonyl compounds. This reaction exhibits a remarkably broad substrate scope and functional group tolerance and provides a useful route to a scarce class of fullerene derivatives, thus building the foundation for exploring their applications in organic electronic research.

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EXPERIMENTAL SECTION

General Procedure for the Synthesis of Products 2a−2aa, 3u, and 3z. A dry 15 mL tube equipped with a magnetic stir bar was charged with C60 (54.0 mg, 0.075 mmol), 1a−1aa (0.15 mmol; for 1l, 0.30 mmol), CuI (2.9 mg, 0.015 mmol), and Ag2O (35.0 mg, 0.15 867

DOI: 10.1021/acs.joc.7b02848 J. Org. Chem. 2018, 83, 862−870

Article

The Journal of Organic Chemistry

relaxation reagent, all 2C unless indicated) δ 156.4 (1C), 156.2 (1C), 150.3 (1C), 148.8, 147.8 (1C), 147.1 (1C), 146.1, 146.0, 145.9, 145.7, 145.69, 145.6, 145.5, 145.3 (1C), 145.0, 144.9, 144.88, 144.8, 144.14, 144.1, 142.8 (1C), 142.6, 142.5, 142.4 (4C), 142.1, 142.05, 141.9, 141.7, 141.3, 140.0, 139.6, 137.2, 135.7, 133.4 (1C), 131.1, 129.2, 128.2 (1C), 127.4 (1C), 127.1 (1C), 124.5 (1C), 124.1 (1C), 123.7 (1C), 122.9 (1C), 120.6 (1C), 120.4 (1C), 111.7 (1C), 111.6 (1C), 111.3 (1C), 99.9 (1C), 78.4 (1C); FT-IR ν/cm−1 (KBr) 1512, 1449, 1195, 1021, 991, 933, 745, 698, 658, 575, 526; UV−vis (CHCl3) λmax/ nm 252, 327, 688; MALDI-TOF MS m/z calcd for C80H12O2 [M]+ 1004.0837, found 1004.0831. Compound 2k: yield 22.7 mg, 27%; brown solid; mp >300 °C; 1H NMR (600 MHz, CDCl3/CS2) δ 8.96 (s, 1H), 8.72 (s, 1H), 8.41 (d, J = 9.0 Hz, 1H), 7.85 (d, J = 7.8 Hz, 1H), 7.73 (d, J = 7.2 Hz, 2H), 7.51 (t, J = 7.2 Hz, 2H), 7.48−7.40 (m, 3H), 4.35 (t, J = 6.6 Hz, 2H), 1.92 (s, 2H), 1.38 (s, 4H), 0.9 (s, 3H); 13C{1H} NMR (150 MHz, CDCl3/ CS2 with Cr(acac)3 as a relaxation reagent, all 2C unless indicated) δ 150.3 (1C), 148.8, 147.7 (1C), 147.0 (1C), 146.0, 145.9, 145.8, 145.6, 145.59, 145.5, 145.4, 145.2, 144.9, 144.86, 144.8, 144.7, 144.0 (4C), 143.5 (1C), 142.5, 142.4, 142.3 (4C), 142.0, 141.97, 141.8, 141.6, 141.5 (1C), 141.2, 140.7 (1C), 139.9, 139.5, 137.1, 135.6, 133.4 (1C), 131.1, 129.1, 128.2 (1C), 127.1 (1C), 122.5 (1C), 122.4 (1C), 122.3 (1C), 121.6 (1C), 120.7 (1C), 117.1 (1C), 111.3 (1C), 109.1 (1C), 108.3 (1C), 99.8 (1C), 78.3 (1C), 43.5 (1C), 29.1 (1C), 28.5 (1C), 22.9 (1C), 13.7 (1C); FT-IR ν/cm−1 (KBr) 2922, 1599, 1510, 1480, 1325, 1238, 1095, 993, 939, 892, 812, 749, 699, 574, 527; UV−vis (CHCl3) λmax/nm 231, 315, 691; MALDI-TOF MS m/z calcd for C85H22N2O3 [M]+ 1118.1630, found 1118.1622. Compound 2l: yield 16.9 mg, 26%; brown solid; mp >300 °C; 1H NMR (600 MHz, CDCl3/CS2) δ 7.50 (d, J = 7.2 Hz, 2H), 7.23 (d, J = 7.2 Hz, 2H), 2.382 (s, 3H), 2.377 (s, 3H); 13C{1H} NMR (150 MHz, CDCl3/CS2 with Cr(acac)3 as a relaxation reagent, all 2C unless indicated) δ 150.4 (1C), 148.3, 146.9 (1C), 146.1 (1C), 145.1, 145.0, 144.9, 144.8, 144.78, 144.75, 144.6, 144.58, 144.1, 144.0, 143.9, 143.8, 143.3, 143.2, 141.9 (1C), 141.7, 141.6, 141.5 (3C), 141.2, 141.1, 141.0, 140.8, 140.4, 139.1, 138.7, 136.4 (1C), 136.0, 134.6, 129.5, 128.8 (1C), 128.6, 110.7 (1C), 99.6 (1C), 76.1 (1C), 20.6 (1C), 12.1 (1C); FT-IR ν/cm−1 (KBr) 2920, 1660, 1454, 1429, 1375, 1238, 1168, 1105, 1020, 961, 805, 747, 658, 569, 526; UV−vis (CHCl3) λmax/nm 259, 314, 692; MALDI-TOF MS m/z calcd for C70H10O [M]+ 866.0726, found 866.0712. Compound 2m: yield 27.9 mg, 43%; brown solid; mp >300 °C; 1H NMR (600 MHz, CDCl3/CS2) δ 8.44 (d, J = 7.2 Hz, 2H), 7.69−7.67 (m, 3H); the 13C NMR spectrum of 2m could not be obtained because of poor solubility of the product; FT-IR ν/cm−1 (KBr) 2201, 1573, 1493, 1446, 1329, 1261, 1095, 922, 806, 768, 649, 575, 551, 526; UV−vis (CHCl3) λmax/nm 252, 316, 452, 685; MALDI-TOF MS m/z calcd for C69H5NO [M]+ 863.0366, found 863.0345. Compound 2n: yield 17.8 mg, 27%; brown solid; mp >300 °C; 1H NMR (600 MHz, CDCl3/CS2) δ 8.40 (d, J = 9.0 Hz, 2H), 7.14 (d, J = 9.0 Hz, 2H), 3.97 (s, 3H); 13C{1H} NMR (150 MHz, CDCl3/CS2 with Cr(acac)3 as a relaxation reagent, all 2C unless indicated) δ 166.1 (1C), 162.9 (1C), 148.2 (1C), 147.4 (1C), 147.1, 146.4, 146.3, 146.1, 146.0 (4C), 145.7, 145.4, 145.2, 145.04, 145.0, 144.5, 144.4, 144.1, 142.9, 142.8, 142.7, 142.66, 142.5, 142.2, 142.17 (4C), 141.9, 141.5, 140.7, 139.8, 137.6, 135.9, 129.9, 119.3 (1C), 116.2 (1C), 114.5, 103.4 (1C), 84.1 (1C), 72.4 (1C), 55.4 (1C); FT-IR ν/cm−1 (KBr) 2830, 2200, 1727, 1606, 1511, 1338, 1263, 1180, 1115, 950, 923, 832, 698, 550, 527; UV−vis (CHCl3) λmax/nm 250, 319, 686; MALDI-TOF MS m/z calcd for C70H7NO2 [M]+ 893.0471, found 893.0458. Compound 2o: yield 28.8 mg, 44%; brown solid; mp >300 °C; 1H NMR (600 MHz, CDCl3/CS2) δ 8.49−8.47 (m, 2H), 7.37−7.34 (m, 2H); the 13C NMR spectrum of 2o could not be obtained because of poor solubility of the product; FT-IR ν/cm−1 (KBr) 2203, 1625, 1599, 1508, 1330, 1240, 1159, 1096, 1003, 950, 919, 840, 647, 562, 526; UV−vis (CHCl3) λmax/nm 257, 316, 454, 684; MALDI-TOF MS m/z calcd for C69H4FNO [M]+ 881.0277, found 881.0266. Compound 2p: yield 33.7 mg, 48%; brown solid; mp >300 °C; 1H NMR (600 MHz, CDCl3/CS2) δ 8.35 (d, J = 8.4 Hz, 2H), 7.83 (d, J = 8.4 Hz, 2H); 13C{1H} NMR (150 MHz, DMSO-d6/CS2 with

121.9 (1C), 113.4, 110.3 (1C), 99.5 (1C), 78.1 (1C), 54.8 (1C); FTIR ν/cm−1 (KBr) 2920, 1723, 1678, 1603, 1511, 1454, 1432, 1254, 1167, 1071, 1032, 1006, 833, 747, 698, 526; UV−vis (CHCl3) λmax/ nm 256, 324, 691; MALDI-TOF MS m/z calcd for C75H12O2 [M]+ 944.0832, found 944.0812. Compound 2f: yield 29.7 mg, 40%; brown solid; mp >300 °C; 1H NMR (600 MHz, CDCl3/CS2) δ 8.29 (d, J = 9.0 Hz, 2H), 7.88 (d, J = 9.0 Hz, 2H), 7.67 (d, J = 8.4 Hz, 2H), 6.92 (d, J = 8.4 Hz, 2H), 3.87 (s, 3H); 13C{1H} NMR (150 MHz, CDCl3/CS2 with Cr(acac)3 as a relaxation reagent, all 2C unless indicated) δ 160.9 (1C), 152.6 (1C), 148.3, 148.1 (1C), 147.4, 146.3, 146.2, 146.1, 146.0, 145.97, 145.6, 145.4, 145.3, 145.1, 145.07, 145.06, 144.9, 144.4, 144.3, 142.9, 142.72, 142.7, 142.6, 142.3, 142.28, 142.1, 141.8, 141.6, 141.3 (1C), 140.3, 139.9, 137.3, 136.1, 132.0, 129.8, 124.3, 121.3 (1C), 114.0, 108.8 (1C), 100.7 (1C), 77.5 (1C), 55.3 (1C); FT-IR ν/cm−1 (KBr) 2922, 1708, 1598, 1512, 1454, 1341, 1255, 1175, 1106, 1031, 749, 688, 562, 527; UV−vis (CHCl3) λmax/nm 255, 316, 684; MALDI-TOF MS m/z calcd for C75H11NO4 [M]+ 989.0683, found 989.0671. Compound 2g: yield 30.8 mg, 41%; brown solid; mp >300 °C; 1H NMR (600 MHz, CDCl3/CS2) δ 8.36 (d, J = 7.8 Hz, 2H), 8.28 (d, J = 7.8 Hz, 2H), 7.93 (d, J = 7.8 Hz, 2H), 7.88 (d, J = 7.8 Hz, 2H); 13 C{1H} NMR (150 MHz, CDCl3/CS2 with Cr(acac)3 as a relaxation reagent, all 2C unless indicated) δ 150.1 (1C), 148.1 (1C), 148.0 (1C), 147.9 (1C), 147.3 (1C), 147.0, 146.3, 146.2, 146.1, 146.0, 145.9, 145.4, 145.3, 145.1, 145.04, 145.0, 144.6, 144.2, 144.1, 144.09, 142.8, 142.7, 142.66, 142.3, 142.24, 142.2, 142.0, 141.6, 141.5, 140.3, 139.9, 139.5 (1C), 137.1, 136.2, 135.0 (1C), 131.7, 128.8, 124.6, 123.7, 114.4 (1C), 100.7 (1C), 76.8 (1C); FT-IR ν/cm−1 (KBr) 1597, 1520, 1343, 1095, 993, 857, 799, 749, 700, 527; UV−vis (CHCl3) λmax/nm 250, 314, 686; MALDI-TOF MS m/z calcd for C74 H8N 2O5 [M] + 1004.0428, found 1004.0403. Compound 2h: yield 27.5 mg, 32%; brown solid; mp >300 °C; 1H NMR (600 MHz, CDCl3/CS2) δ 8.44 (s, 1H), 7.87 (d, J = 8.4 Hz, 1H), 7.80 (d, J = 8.4 Hz, 2H), 7.55 (d, J = 7.8 Hz, 1H), 7.39−7.36 (m, 1H), 7.35−7.32 (m, 2H), 7.29−7.27 (m, 1H), 7.25 (d, J = 8.4 Hz, 2H), 7.19−7.16 (m, 1H), 6.98 (t, J = 7.2 Hz, 1H), 2.40 (s, 3H); 13 C{1H} NMR (150 MHz, CDCl3/CS2with Cr(acac)3 as a relaxation reagent, all 1C unless indicated) δ 150.6, 147.9, 147.8, 147.6, 147.2, 146.3, 146.28 (3C), 146.2, 146.1, 146.0, 145.9, 145.87, 145.8, 145.77, 145.4, 145.37, 145.35, 145.3, 145.14, 145.1, 145.0, 144.9, 144.86, 144.8, 144.6, 144.57, 144.3, 144.2, 144.19, 144.18, 144.1, 143.7, 143.4, 142.8, 142.75, 142.6, 142.58, 142.57, 142.5, 142.4, 142.2 (3C), 142.17, 142.1, 142.0, 141.9, 141.6, 141.5, 141.4, 141.3, 140.2, 140.18, 139.8, 139.77, 137.6, 137.1, 135.8, 135.76, 135.6, 133.6, 132.9, 132.8, 130.8, 130.1, 130.0, 129.6 (2C), 127.5 (3C), 126.5, 124.2, 121.7, 120.0, 114.5, 100.8, 76.7, 21.6; FT-IR ν/cm−1 (KBr) 2920, 1598, 1493, 1454, 1433, 1343, 1167, 1090, 1034, 987, 899, 813, 751, 667, 566, 527; UV−vis (CHCl3) λmax/nm 269, 317, 690; MALDI-TOF MS m/z calcd for C81H16BrNO3S [M]+ 1163.0014, found 1162.9992. Compound 2i: yield 19.0 mg, 25%; brown solid; mp >300 °C; 1H NMR (600 MHz, CDCl3/CS2) δ 8.04 (s, 1H), 7.78 (d, J = 7.2 Hz, 1H), 7.73 (s, 2H), 7.69 (d, J = 7.2 Hz, 2H), 7.55 (d, J = 7.2 Hz, 1H), 7.47 (t, J = 7.2 Hz, 2H), 7.42−7.37 (m, 2H), 7.32 (t, J = 7.2 Hz, 1H), 3.92 (s, 2H); 13C{1H} NMR (150 MHz, CDCl3/CS2 with Cr(acac)3 as a relaxation reagent, all 2C unless indicated) δ 150.9 (1C), 149.0, 148.0 (1C), 147.2 (1C), 146.2, 146.1, 146.0, 145.9, 145.8, 145.78, 145.6, 145.5, 145.2, 145.1, 145.0, 144.9, 144.3, 144.27, 143.7 (1C), 143.0 (1C), 142.97 (3C), 142.8, 142.6, 142.6, 142.3, 142.2, 142.0, 141.9, 141.5, 141.0 (1C), 140.2, 139.7, 137.3, 135.9, 133.6 (1C), 131.2, 129.2, 128.2 (1C), 128.1 (1C), 127.2 (1C), 127.0 (1C), 126.9 (1C), 125.1 (1C), 124.5 (1C), 120.2 (1C), 119.6 (1C), 112.1 (1C), 99.9 (1C), 78.5 (1C), 37.1 (1C); FT-IR ν/cm−1 (KBr) 1513, 1449, 1195, 991, 933, 841, 764, 744, 698, 658, 573, 526; UV−vis (CHCl3) λmax/nm 252, 315, 690; MALDI-TOF MS m/z calcd for C81H14O [M]+ 1002.1045, found 1002.1036. Compound 2j: yield 27.0 mg, 36%; brown solid; mp >300 °C; 1H NMR (600 MHz, CDCl3/CS2) δ 8.49 (s, 1H), 7.91 (d, J = 7.2 Hz, 1H), 7.81 (d, J = 8.4 Hz, 1H), 7.72 (d, J = 7.2 Hz, 2H), 7.59 (d, J = 8.4 Hz, 1H), 7.53−7.49 (m, 4H), 7.45 (t, J = 7.2 Hz, 1H), 7.37 (t, J = 7.2 Hz, 1H); 13C{1H} NMR (150 MHz, CDCl3/CS2 with Cr(acac)3 as a 868

DOI: 10.1021/acs.joc.7b02848 J. Org. Chem. 2018, 83, 862−870

Article

The Journal of Organic Chemistry

2C unless indicated) δ 161.5 (1C), 155.1, 149.5, 148.2 (1C), 147.4 (1C), 146.9, 146.5, 146.3, 146.2, 146.1, 146.08, 145.9, 145.5, 145.3, 145.2, 145.1, 145.0, 144.7, 144.3, 143.0, 142.9, 142.8, 142.75, 142.6, 142.4, 142.38, 141.9, 141.89, 140.3, 139.9 (1C), 139.4, 137.8, 135.4, 130.8 (1C), 129.4 (1C), 128.9, 128.8, 128.7, 124.0 (1C), 120.1 (1C), 109.7 (1C), 101.1 (1C), 75.2 (1C); FT-IR ν/cm−1 (KBr) 1657, 1636, 1593, 1528, 1494, 1438, 1336, 1243, 1119, 1072, 1005, 952, 929, 798, 750, 690, 562, 526; UV−vis (CHCl3) λmax/nm 247, 317, 488, 544, 684; MALDI-TOF MS m/z calcd for C75H11NO2 [M]+ 957.0784, found 957.0766. Compound 2cc: yield 18.6 mg, 24%; brown solid; mp >300 °C; 1H NMR (600 MHz, CDCl3/CS2) δ 8.08 (d, J = 6.6 Hz, 2H), 7.87 (d, J = 8.4 Hz, 2H), 7.69−7.66 (m, 3H), 7.50 (s, 1H), 7.30 (d, J = 8.4 Hz, 2H), 4.28 (q, J = 7.2 Hz, 2H), 1.34 (t, J = 7.2 Hz, 3H); 13C{1H} NMR (150 MHz, DMSO-d6/CS2 with Cr(acac)3 as a relaxation reagent, all 2C unless indicated) δ 163.8 (1C), 161.0 (1C), 154.7 (1C), 148.2, 147.1 (1C), 146.2, 145.6, 145.3, 145.2, 145.0, 144.95, 144.9, 144.7, 144.4, 144.1, 144.0 (4C), 143.7, 143.6, 143.1, 141.8, 141.7, 141.6, 141.57, 141.4, 141.3, 141.2, 140.74, 140.7, 139.1, 138.8, 136.6, 134.3, 129.9 (1C), 129.4, 128.1 (1C), 127.9, 127.6, 124.3 (1C), 118.1, 108.2 (1C), 100.1 (1C), 74.0 (1C), 59.5 (1C), 14.0 (1C); FT-IR ν/cm−1 (KBr) 2922, 1717, 1670, 1575, 1519, 1405, 1331, 1275, 1173, 1106, 1023, 928, 767, 693, 562, 527; UV−vis (CHCl3) λmax/nm 258, 316, 454, 684; MALDI-TOF MS m/z calcd for C78H15NO4 [M] + 1029.0996, found 1029.1012. Compound 2dd: yield 14.5 mg, 20%; brown solid; mp >300 °C; 1H NMR (600 MHz, CDCl3/CS2) δ 8.06−8.05 (m, 2H), 7.63−7.62 (m, 3H), 5.63 (d, J = 7.2 Hz, 1H), 3.90−3.89 (m, 1H), 1.91−1.89 (m, 2H), 1.62−1.57 (m, 3H), 1.38−1.33 (m, 2H), 1.15−1.09 (m, 1H), 1.04−0.99 (m, 2H); 13C{1H} NMR (150 MHz, CDCl3/CS2 with Cr(acac)3 as a relaxation reagent, all 2C unless indicated) δ 162.3 (1C), 157.4 (1C), 148.5, 147.9 (1C), 147.1 (1C), 146.9, 146.2, 146.0, 145.9, 145.8, 145.7, 145.5, 145.2, 145.0, 144.8, 144.7, 144.4, 144.2, 144.0, 142.6, 142.55, 142.5, 142.3, 142.28, 142.1, 142.0, 141.5, 141.4, 139.7, 139.67, 137.3, 135.1, 131.0, 129.1, 128.8, 128.7 (1C), 108.5 (1C), 101.3 (1C), 74.2 (1C), 48.2 (1C), 32.7, 25.7 (1C), 24.9 (1C); FT-IR ν/cm−1 (KBr) 2923, 2848, 1789, 1649, 1623, 1503, 1446, 1336, 1141, 1005, 953, 747, 689, 562, 526; UV−vis (CHCl3) λmax/nm 250, 315, 452, 685; MALDI-TOF MS m/z calcd for C75H17NO2 [M]+ 963.1259, found 963.1268. Compound 2ee: yield 27.1 mg, 41%; brown solid; mp >300 °C; 1H NMR (600 MHz, CDCl3/CS2) δ 8.17 (d, J = 7.2 Hz, 1H), 7.81−7.78 (m, 1H), 7.60 (d, J = 8.4 Hz, 1H), 7.55−7.53 (m, 1H); the 13C NMR spectrum of 2ee could not be obtained because of poor solubility of the product; FT-IR ν/cm−1 (KBr) 1728, 1647, 1507, 1397, 1163, 1099, 1027, 897, 815, 747, 563, 526; UV−vis (CHCl3) λmax/nm 260, 317, 452, 682; MALDI-TOF MS m/z calcd for C69H4O3 [M]+ 880.0160, found 880.0145. Compound 3u: yield 18.3 mg, 29%; brown solid; mp >300 °C; 1H NMR (600 MHz, CDCl3/CS2) δ 2.72 (s, 3H); 13C{1H} NMR (150 MHz, CDCl3/CS2 with Cr(acac)3 as a relaxation reagent, all 2C unless indicated) δ 161.6 (1C), 145.3, 145.25, 145.2, 145.1, 145.03 (4C), 145.01, 144.8, 144.6, 144.59, 144.5, 144.3, 144.2 (1C), 144.1 (1C), 143.8, 143.7, 143.3, 143.0, 142.9, 142.9, 142.7, 142.03, 142.0, 141.9 (4C), 141.6, 141.3, 141.1, 140.9, 138.7, 112.4 (1C), 69.3, 54.4 (1C), 34.5 (1C); FT-IR ν/cm−1 (KBr) 2946, 2244, 1790, 1755, 1508, 1429, 1257, 1101, 1001, 813, 740, 716, 556, 526; UV−vis (CHCl3) λmax/nm 260, 316, 685; MALDI-TOF MS m/z calcd for C64H3NO2 [M]+ 817.0158, found 817.0146. Compound 3z: yield 24.1 mg, 37%; brown solid; mp >300 °C; 1H NMR (400 MHz, CDCl3/CS2) δ 8.20 (d, J = 8.4 Hz, 2H), 8.00 (d, J = 8.4 Hz, 2H); the 13C NMR spectrum of 3z could not be obtained because of poor solubility of the product; FT-IR ν/cm−1 (KBr) 1712, 1590, 1514, 1427, 1349, 1265, 1229, 1042, 738, 700, 575, 526; UV−vis (CHCl3) λmax/nm 253, 327, 426, 685; MALDI-TOF MS m/z calcd for C69H4O2 [M]+ 864.0206, found 864.0189.

Cr(acac)3 as a relaxation reagent, all 2C unless indicated) δ 163.7 (1C), 147.3 (1C), 146.5 (1C), 145.6, 145.5, 145.47, 145.3, 145.2 (4C), 144.9, 144.4, 144.3, 144.2, 144.1, 143.5 (4C), 143.3, 142.0, 141.9 (4C), 141.6, 141.58, 141.4 (3C), 141.3 (3C), 141.0, 140.6, 139.8, 139.0, 136.7, 135.1, 131.9 128.6, 127.2 (1C), 125.0 (1C), 113.9 (1C), 101.8 (1C), 86.3 (1C), 71.7 (1C); FT-IR ν/cm−1 (KBr) 2204, 1624, 1587, 1511, 1487, 1399, 1327, 1153, 1096, 1001, 918, 829, 766, 716, 647, 562, 526; UV−vis (CHCl3) λmax/nm 252, 316, 684; MALDI-TOF MS m/z calcd for C69H4BrNO [M]+ 940.9476, found 940.9461. Compound 2q: yield 27.0 mg, 39%; brown solid; mp >300 °C; 1H NMR (600 MHz, CDCl3/CS2) δ 8.55 (d, J = 8.4 Hz, 2H), 8.34 (d, J = 8.4 Hz, 2H), 4.03 (s, 3H); 13C{1H} NMR (150 MHz, CS2/CDCl3 with Cr(acac)3 as a relaxation reagent, all 2C unless indicated) δ 165.7 (1C), 165.3 (1C), 148.2 (1C), 147.5 (1C), 146.46, 146.4, 146.3, 146.2, 146.1, 146.06, 145.8, 145.3, 145.2, 145.1, 145.0, 144.4 (4C), 144.2, 142.8, 142.77, 142.7, 142.4, 142.3, 142.27, 142.2 (4C), 141.9, 141.5, 140.7, 139.9, 137.6, 136.0, 133.5 (1C), 130.7 (1C), 130.2, 127.9, 115.4 (1C), 103.0 (1C), 88.2 (1C), 72.4 (1C), 52.4 (1C); FT-IR ν/cm−1 (KBr) 2945, 2206, 1727, 1625, 1512, 1433, 1408, 1276, 1108, 1002, 919, 861, 774, 700, 563, 527; UV−vis (CHCl3) λmax/nm 253, 317, 456, 684; MALDI-TOF MS m/z calcd for C71H7NO3 [M]+ 921.0420, found 921.0403. Compound 2r: yield 26.6 mg, 41%; brown solid; mp >300 °C; 1H NMR (600 MHz, CDCl3/CS2) δ 8.31 (s, 1H), 7.78 (s, 1H), 7.37 (s, 1H); the 13C NMR spectrum of 2r could not be obtained because of poor solubility of the product; FT-IR ν/cm−1 (KBr) 2201, 1614, 1416, 1373, 1092, 1057, 993, 947, 906, 712, 656, 563, 552, 526; UV−vis (CHCl3) λmax/nm 251, 316, 685; MALDI-TOF MS m/z calcd for C67H3NOS [M]+ 868.9935, found 868.9923. Compound 2s: yield 24.2 mg, 38%; brown solid; mp >300 °C; 1H NMR (600 MHz, CDCl3/CS2) δ 7.87 (d, J = 1.8 Hz, 1H), 7.49 (d, J = 3.6 Hz, 1H), 6.78 (dd, J = 3.6, 1.8 Hz, 1H); the 13C NMR spectrum of 2s could not be obtained because of poor solubility of the product; FT-IR ν/cm−1 (KBr) 2206, 1658, 1432, 1327, 1221, 1186, 945, 924, 748, 553, 527; UV−vis (CHCl3) λmax/nm 251, 318, 684; MALDI-TOF MS m/z calcd for C67H3NO2 [M]+ 853.0158, found 853.0129. Compound 2t: yield 22.3 mg, 37%; brown solid; mp >300 °C; 1H NMR (600 MHz, CDCl3/CS2) δ 2.72 (s, 3H); 13C{1H} NMR (150 MHz, CDCl3/CS2 with Cr(acac)3 as a relaxation reagent, all 2C unless indicated) δ 169.5 (1C), 147.5 (1C), 146.7 (1C), 146.1, 145.8, 145.7, 145.5, 145.4 (4C), 145.1, 144.7, 144.5, 144.4, 144.3, 143.7 (4C), 143.5, 142.2, 142.1, 142.05, 141.9, 141.8, 141.6, 141.5 (4C), 141.2, 140.8, 140.0, 139.2, 136.9, 135.2, 113.5 (1C), 103.4 (1C), 89.2 (1C), 70.8 (1C), 13.9 (1C); FT-IR ν/cm−1 (KBr) 2920, 2212, 1574, 1519, 1380, 1277, 1016, 931, 773, 680, 594, 526; UV−vis (CHCl3) λmax/nm 252, 329, 683; MALDI-TOF MS m/z calcd for C64H3NO [M]+ 801.0209, found 801.0200. Compound 2v: 7 yield 12.0 mg, 18%; brown solid; mp >300 °C; 1H NMR (600 MHz, CDCl3/CS2) δ 8.11−8.10 (m, 2H), 7.60−7.59 (m, 3H), 4.26 (q, J = 7.2 Hz, 2H), 1.17 (t, J = 7.2 Hz, 3H). Compound 2w: 6a yield 12.1 mg, 19%; brown solid; mp >300 °C; 1 H NMR (600 MHz, CDCl3/CS2) δ 4.35 (q, J = 7.2 Hz, 2H), 2.87 (s, 3H), 1.32 (t, J = 7.2 Hz, 3H). Compound 2x:.6a,7a yield 14.7 mg, 24%; brown solid; mp >300 °C; 1 H NMR (600 MHz, CDCl3/CS2) δ 2.92 (s, 3H), 2.70 (s, 3H). Compound 2y: 7 yield 22.3 mg, 36%; brown solid; mp >300 °C; 1H NMR (600 MHz, CDCl3/CS2) δ 3.14 (t, J = 6.4 Hz, 2H), 2.72 (t, J = 6.4 Hz, 2H), 2.50−2.46 (m, 2H). Compound 2aa: yield 14.3 mg, 20%; brown solid; mp >300 °C; 1H NMR (600 MHz, CDCl3/CS2) δ 7.86 (d, J = 7.8 Hz, 2H), 7.70 (d, J = 7.2 Hz, 2H), 7.36−7.33 (m, 2H), 7.28−7.26 (m, 2H), 7.23−7.21 (m, 2H); the 13C NMR spectrum of 2aa could not be obtained because of poor solubility of the product; FT-IR ν/cm−1 (KBr) 1620, 1594, 1444, 1337, 1149, 1096, 1006, 923, 889, 806, 718, 690, 562, 526; UV−vis (CHCl3) λmax/nm 256, 316, 454, 683; MALDI-TOF MS m/z calcd for C75H10O2 [M]+ 942.0675, found 942.0649. Compound 2bb: yield 17.3 mg, 24%; brown solid; mp >300 °C; 1H NMR (400 MHz, DMSO-d6/CS2) δ 8.12−8.09 (m, 2H), 7.63−7.58 (m, 5H), 7.25−7.21 (m, 2H), 7.04−7.01 (m, 1H); 13C{1H} NMR (150 MHz, DMSO-d6/CS2 with Cr(acac)3 as a relaxation reagent, all 869

DOI: 10.1021/acs.joc.7b02848 J. Org. Chem. 2018, 83, 862−870

Article

The Journal of Organic Chemistry

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.joc.7b02848. UV−vis spectra, CVs of representative compounds, and NMR spectra of products 2a−2ee, 3u, and 3z (PDF)

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. *E-mail: [email protected]. ORCID

Tong-Xin Liu: 0000-0003-2321-8208 Zhiguo Zhang: 0000-0001-6920-0471 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We are grateful to the NSFC (nos. 21302044, U1304524, and U1604285), China Postdoctoral Science Foundation Funded Project (2015T80769), Program for Science & Technology Innovation Talents in Universities of Henan Province (18HASTIT006), the 111 Project (D17007), Key Project of Henan Educational Committee (18A150009), and Outstanding Youth Science Project Funding of Henan Normal University (14YQ004) for financial support.

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DOI: 10.1021/acs.joc.7b02848 J. Org. Chem. 2018, 83, 862−870