Preparation of 2-Amino-5-homoallylfurans via Palladium-Catalyzed

Sep 26, 2017 - Stepanovs, D.; Turks, M.; Vogel, P. Chem. - Eur. J. 2016, 22, 4196. (b) McAtee, J. R.; Yap, G. P. A.; Watson, D. A. J. Am. Chem. Soc. 2...
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Cite This: J. Org. Chem. 2017, 82, 11134-11140

Preparation of 2‑Amino-5-homoallylfurans via Palladium-Catalyzed Tandem Cycloisomerization/Heck-Type Coupling of Homoallenyl Amides with Allyltrialkylsilanes Jian Zhang, Mingchang Wu, Wei Lu, Shuaifeng Wang, Yan Zhang, Cungui Cheng,* and Gangguo Zhu* Department of Chemistry, Zhejiang Normal University, 688 Yingbin Road, Jinhua 321004, China S Supporting Information *

ABSTRACT: The direct access to 2-amino-5-homoallylfurans has been realized by a palladium-catalyzed tandem cycloisomerization/Heck-type coupling between homoallenyl amides and allyltrialkylsilanes, using a novel DDQ/MnO2 combination as the efficient oxidant. The reaction exclusively affords γ-allylation products in good to excellent yields with broad substrate scope under exceptionally mild reaction conditions. It represents one of the rare examples of the Pd-catalyzed intermolecular Heck-type coupling of allytrialkylsilanes terminated by β-silyl elimination, thus complementing traditional allylation methods because of the excellent γ-selectivity.

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INTRODUCTION Furan is an important five-membered heterocycle commonly found in chemical, material, and biological research.1 In particular, 2-aminofurans have attracted numerous attention since they can serve as effective antibacterial agents,2 highly potent inhibitors for activated cdc42-associated tyrosine kinase 1 (ACK1),3 glycogen synthase kinase-3,4 receptor interacting protein 1 (RIP1) kinase,5 and furanopyrimidine Aurora kinase.6 Meanwhile, 2-aminofurans are versatile synthetic intermediates in organic synthesis.7 As such, a number of methods have been developed for their preparation, including the coupling of αbromoacetophenones with malononitrile,8 Stetter-γ-keto nitrile cyclization between acylidenemalononitriles and aryl aldehydes,9 three-component reaction of isocyanides, activated alkynes, and carbonyl compounds,10 Cu-catalyzed [3 + 2] cycloaddition of carbenoids with enamines,11 Au- or Rhcatalyzed transformation of ynamides,12 Cu-catalyzed direct amidation of furans,13 iodine-promoted reaction of 1cyanocyclopropane 1-esters,14 and Au-catalyzed cycloisomerization of allenyl amides.15 Despite progress, the development of new efficient protocols for the straightforward assembly of 2aminofurans, especially 3,4,5-trisubstituted ones, is still highly desirable. To this end, we have recently developed a methodology for the one-pot and divergent synthesis of 2-aminofurans,16 which proceeds via a furfurylpalladium intermediate I resulting from the Pd(II)-catalyzed cycloisomerization of homoallenyl amides 1. Specifically, the protonolysis of C−Pd bond of I gives 2amino-5-alkylfurans together with regeneration of Pd(II) catalyst (Scheme 1, path a), while a radical-type oxidation of I under an air atmosphere selectively forms 2-amino-5formylfurans (path b). Through a Pd(II)/Pd(IV) catalytic cycle, a series of heteroatom-substituted products can be © 2017 American Chemical Society

generated using hypervalent iodine organic compounds as the oxidants (path c). To further expand the scope of this methodology, we envisioned that quenching the C−Pd bond of I with alkene components like allyltrialkylsilanes would provide an alkylpalladium intermediate II (path d). Subsequently, the Pd-SiR3 elimination17−19 may lead to the allylation product, along with the release of R3SiX and Pd(0), which can be oxidized to Pd(II) for the next catalytic cycle. In this paper, we report the successful development of such a Pd-catalyzed tandem cycloisomerization/Heck-type coupling of homoallenyl amides with bench-stable and readily available allyltrialkylsilanes as the alkene component. The reaction provides 2-amino5-homoallylfurans in high yields with good functional group compatibility under very mild reaction conditions. Notably, compared with the traditional Heck reaction terminated by β-H elimination, the silane-terminated Heck reaction has been much less explored. Although Tietze and co-workers have successfully developed the intramolecular Heck reaction of allyltrialkylsilanes,18 the intermolecular version is more challenging and remains largely unexplored. To the best of our knowledge, the only example came from the work of Jeffery,19 in which the Pdcatalyzed arylation of allyltrimethylsilanes was described, unfortunately, the substrate scope was very limited (only three substrates). Therefore, our work represents a significant advance on the development of general and efficient Pdcatalyzed intermolecular Heck-type reaction of allyltrialkylsilanes featuring the termination by β-silyl elimination. Received: August 22, 2017 Published: September 26, 2017 11134

DOI: 10.1021/acs.joc.7b02131 J. Org. Chem. 2017, 82, 11134−11140

Article

The Journal of Organic Chemistry

Scheme 1. Our Attempts at Divergent Synthesis of 2-Aminofurans via Pd-Catalyzed Cyclization of Homoallenyl Amides

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RESULTS AND DISCUSSION Our initial screening shown in Table 1 commenced with the reaction between homoallenyl amide 1a and allyltrimethylsilane (2a). After a number of efforts, 65% yield of 3a was obtained by running the reaction with 10 mol % of PdBr2, 20 mol % of 2,3dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), and 3 equiv of MnO220 in MeCN at 25 °C for 12 h (Table 1, entry 1). The

utilization of NFSI, selectfluor, or PhI(O2CCF3)2 as the oxidant failed to provide the desired product 3a (entries 2−4). Although the employment of CuBr2 as the oxidant enabled a reasonable yield, other oxidants including Ag2O, BQ, and O2 led to inferior results (entries 5−10). Choosing MeCN as the solvent was crucial for the reaction, as replacing MeCN by ClCH2CH2Cl, THF, or DMF shut down the transformation (entries 11−13). We also investigated the effect of silyl groups on the reaction. When silyl groups such as SiEt3, SiMe2(t-Bu), and SiMe2Ph were used in place of SiMe3, the reaction efficiency was improved to some extent (entries 14−17). Specifically, using allyltriethylsilane (2b) as the allylation reagent led to a highest yield, giving 3a in 76% yield. The scale-up experiment (2 mmol) gave a comparable yield of 78%. Of note, the addition of 20 mol % of DDQ was essential for the reaction (entry 18). Other palladium sources such as PdCl2 and Pd(OAc)2 proved to be less effective for the reaction (entries 19 and 20). With the optimized reaction conditions in hand, we then evaluated the reactivity of various homoallenyl amides using 2b as the coupling partner (Scheme 2). The successful production of 3b−3e in high yields with intact fluoro, chloro, and bromo atoms offers good opportunities for the downstream derivatizations. Particularly, para- and ortho-substituted substrates 1c and 1d reacted with 2b smoothly to afford the corresponding products 3c and 3d in 75% and 80% yield, respectively, indicating that the substitution pattern of the benzene ring had little impact on the reaction. Both electron-rich and -deficient substrates were suitable for the 2-amino-5-homoallylfuran formation (3f−3i). Likewise, the reaction could be extended to homoallenyl amides with heteroaryl, alkenyl, or alkyl substituents at the C2 position of 1, providing 3j−3l in high yields. Substitution of the C3 position with aryl or alkyl groups was also feasible (3q and 3r). The introduction of a methyl group at the C5 position of 1 resulted in the formation of 3s in a moderate yield, while no detectable product 3t was observed when 1t was employed as the starting material. It is likely that the Pd-catalyzed intermolecular Heck-type reaction of allyltrialkylsilanes is retarded by steric effects of the C−Pd bond of the intermediate I (Scheme 1). Overall, indications of good functional group tolerance can be found from 2-amino-5-homoallylfurans thus

Table 1. Optimization of Reaction Conditionsa

entry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21

deviations from standard conditions none NFSI instead of DDQ/MnO2 selectfluor instead of DDQ/MnO2 PhI(O2CCF3)2 instead of DDQ/ MnO2 CuBr2 instead of DDQ/MnO2 Cu(OAc)2 instead of DDQ/MnO2 Ag2O instead of DDQ/MnO2 BQ instead of DDQ/MnO2 Cl4−BQ instead of DDQ/MnO2 O2 instead of DDQ/MnO2 ClCH2CH2Cl instead of MeCN THF instead of MeCN DMF instead of MeCN none none none none without addition of DDQ PdCl2 instead of PdBr2 Pd(OAc)2 instead of PdBr2 PhCN instead of MeCN

2/Si 2a/SiMe3 2a/SiMe3 2a/SiMe3 2a/SiMe3 2a/SiMe3 2a/SiMe3 2a/SiMe3 2a/SiMe3 2a/SiMe3 2a/SiMe3 2a/SiMe3 2a/SiMe3 2a/SiMe3 2b/SiEt3 2c/SiMe2(t-Bu) 2d/Si(i-Pr)3 2e/SiMe2Ph 2b/SiEt3 2b/SiEt3 2b/SiEt3 2b/SiEt3

yield (%)b 65 trace trace trace 51 19 15 31 44 42 trace trace trace 76 (78)c 68 61 72 nr 42 12 33

a

Reaction conditions: 1a (0.2 mmol), 2 (0.4 mmol), PdBr2 (10 mol %), DDQ (0.04 mmol), MnO2 (0.6 mmol), MeCN (2 mL), under N2, 25 °C, 12 h. bIsolated yield. cYield of 2 mmol scale. BQ = 1,4benzoquinone. nr = no reaction. 11135

DOI: 10.1021/acs.joc.7b02131 J. Org. Chem. 2017, 82, 11134−11140

Article

The Journal of Organic Chemistry Scheme 2. Scope of Homoallenyl Amidesa

Reaction conditions: 1 (0.2 mmol), 2b (0.4 mmol), PdBr2 (10 mol %), DDQ (0.04 mmol), MnO2 (0.6 mmol), MeCN (2 mL), under N2, 25 °C, 12 h with isolated yields.

a

Based on the above results and previous reports,17−19 a plausible mechanism for this Pd-catalyzed tandem cycloisomerization/Heck-type coupling of homoallenyl amides has been proposed in Scheme 4. The oxypalladation of 1, followed by a deprotonation affords a furfurylpalladium intermediate I, which is transformed to the alkylpalladium species II via the carbopalladation of allyltrialkylsilanes 2. Then, the β-silyl elimination forms γ-allylation products 3 with the release of R3SiX and Pd(0), which can be oxidized to Pd(II) by the DDQ/MnO2 combination. In this case, DDQ seems to act as an electron-transfer mediator, which in turn is reoxidized by MnO2, the terminal oxidant.

obtained, which is attractive for the synthetic application. The formation of 2-amino-5-homoallylfurans was determined by the X-ray diffraction analysis of product 3n.21 In the meantime, the allyltrialkylsilane component was also varied, and the results are summarized in Scheme 3. In particular, the Pd-catalyzed tandem cycloisomerization/allylation of 1a with 2f took place efficiently to give 3u in 79% yield, albeit at a slightly elevated reaction temperature (50 °C). For allyltrimethylsilane 2h, the reaction afforded the γ-allylation product 3w in 78% yield, and no α-allylation product was detected. Furthermore, the reaction of 2i exclusively produced the γ-allylation product 3x in 88% yield, while the γ-allylation products 3y and 3z were obtained when 2j and 2k were employed as the coupling partners. These results indicated that the β-SiR3 elimination, rather than the formation of an allylpalladium intermediate, is involved in this reaction. Additionally, the more sterically demanding allyltrialkylsilanes, including 2l, 2m, and 2n, were also competent substrates for this tandem process, although a moderate yield was observed for the reaction of 2n (3aa−3ac). Remarkably, in the case of 2o, the reaction selectively produced the desilylation product 3ad in 78% yield, although the β-OAc elimination is also feasible in Pd-catalyzed Heck-type reaction,22 thus highlighting the excellent chemoselectivity of this reaction. Similar results were observed for the substrate 2p, with an allylic hydroxy group (3ae).

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CONCLUSION

In conclusion, we have developed a novel Pd-catalyzed tandem cycloisomerization/allylation of homoallenyl amides with bench-stable and readily available allyltrialkylsilanes as the allylation reagent, which exclusively affords γ-allylation products in good to excellent yields with broad substrate scope under very mild reaction conditions. A new combination comprising the catalytic DDQ and excess of MnO2 proves to be the efficient oxidant for converting Pd(0) into Pd(II). The work described here constitutes one of the very rare examples on the Pd-catalyzed intermolecular Heck-type reaction of allyltrialkylsilanes terminating by β-silyl elimination, thus providing a good 11136

DOI: 10.1021/acs.joc.7b02131 J. Org. Chem. 2017, 82, 11134−11140

Article

The Journal of Organic Chemistry Scheme 3. Scope of Allylsilanesa

analyses were conducted using a TOF MS instrument with an ESI source. Flash column chromatography was performed with silica gel (300−400 mesh) using petroleum ether/EtOAc as the eluent. Allyltrialkylsilanes were either obtained from commercial sources or prepared according to the methods reported in the literature.24 General Procedure for Palladium-Catalyzed Tandem Cycloisomerization/Heck-Type Coupling of Homoallenyl Amides with Allyltrialkylsilanes. To a mixture of 1a (64 mg, 0.2 mmol), DDQ (9 mg, 0.04 mmol), and MnO2 (52 mg, 0.6 mmol) in 2 mL of dry MeCN was added PdBr2 (5.3 mg, 0.02 mmol) under a nitrogen atmosphere. After stirring at room temperature for 12 h, the reaction mixture was quenched with water, extracted with EtOAc, washed with brine, dried over anhydrous Na2SO4, and concentrated. Column chromatography on silica gel (EtOAc/petroleum ether = 1:20) gave 55 mg (yield: 76%) of 3a as a colorless oil. Starting from 1a (642 mg, 2 mmol), 563 mg of 3a (78% yield) was obtained as a colorless oil. 1H NMR (600 MHz, CDCl3) δ 7.46 (d, J = 7.7 Hz, 2H), 7.38 (t, J = 7.7 Hz, 2H), 7.30 (t, J = 7.4 Hz, 1H), 5.88−5.82 (m, 1H), 5.07 (dd, J = 17.1, 1.6 Hz, 1H), 5.01 (dd, J = 10.2, 1.2 Hz, 1H), 3.40 (t, J = 7.1 Hz, 2H), 2.99 (s, 3H), 2.70 (t, J = 7.5 Hz, 2H), 2.39 (q, J = 7.2 Hz, 2H), 1.93 (s, 3H), 1.29−1.24 (m, 2H), 1.12−1.06 (m, 2H), 0.69 (t, J = 7.4 Hz, 3H); 13C NMR (151 MHz, CDCl3) δ 148.6, 138.6, 137.3, 131.7, 129.1, 128.2, 127.2, 124.4, 115.4, 115.3, 50.9, 39.5, 32.4, 30.3, 25.7, 19.5, 13.5, 9.1; HRMS (ESI) calcd for C20H27NNaO3S (M + Na)+ 384.1604, found 384.1604. Compound 3b. 60 mg, 79% yield, colorless oil; 1H NMR (600 MHz, CDCl3) δ 7.47−7.44 (m, 2H), 7.10−7.07 (m, 2H), 5.87−5.81 (m, 1H), 5.06 (dd, J = 17.1, 1.7 Hz, 1H), 5.01 (dd, J = 10.2, 1.6 Hz, 1H), 3.39 (t, J = 7.1 Hz, 2H), 3.04 (s, 3H), 2.69 (t, J = 7.5 Hz, 2H), 2.40−2.37 (m, 2H), 1.91 (s, 3H), 1.25−1.20 (m, 2H), 1.11−1.05 (m, 2H), 0.69 (t, J = 7.4 Hz, 3H); 13C NMR (151 MHz, CDCl3) δ 162.2 (d, J = 246.5 Hz), 148.8, 138.6, 137.2, 130.8 (d, J = 8.1 Hz), 127.7 (d, J = 3.4 Hz), 123.7, 115.5, 115.24, 115.22 (d, J = 21.4 Hz), 50.8, 39.4, 32.4, 30.2, 25.7, 19.5, 13.5, 9.1; 19F NMR (565 MHz, CDCl3) δ −114.9; HRMS (ESI) calcd for C20H26FNNaO3S (M + Na)+ 402.1510, found 402.1517. Compound 3c. 59 mg, 75% yield, colorless oil; 1H NMR (600 MHz, CDCl3) δ 7.45−7.40 (m, 2H), 7.39−7.34 (m, 2H), 5.80−5.87 (m, 1H), 5.12−4.97 (m, 2H), 3.39 (t, J = 7.1 Hz, 2H), 3.04 (s, 3H), 2.69 (t, J = 7.5 Hz, 2H), 2.37−2.40 (m, 2H), 1.91 (s, 3H), 1.27−1.20 (m, 2H), 1.06−1.12 (m, 2H), 0.70 (t, J = 7.4 Hz, 3H); 13C NMR (151 MHz, CDCl3) δ 148.9, 138.8, 137.2, 133.3, 130.5, 130.2, 128.5, 123.6, 115.5, 115.2, 50.8, 39.4, 32.4, 30.3, 25.7, 19.5, 13.5, 9.2; HRMS (ESI) calcd for C20H26ClNNaO3S (M + Na)+ 418.1214, found 418.1218. Compound 3d. 63 mg, 80% yield, colorless oil; 1H NMR (600 MHz, CDCl3) δ 7.57−7.55 (m, 1H), 7.43−7.40 (m, 1H), 7.31−7.26 (m, 2H), 5.88−5.81 (m, 1H), 5.06 (dd, J = 17.1, 1.5 Hz, 1H), 5.01 (d, J = 10.2 Hz, 1H), 3.43−3.33 (m, 2H), 3.02 (s, 3H), 2.70 (t, J = 7.4 Hz, 2H), 2.41−2.38 (m, 2H), 1.81 (s, 3H), 1.37−1.31 (m, 2H), 1.12−1.03 (m, 2H), 0.74 (t, J = 7.4 Hz, 3H); 13C NMR (151 MHz, CDCl3) δ 148.3, 138.9, 137.2, 134.0, 132.9, 130.8, 129.3, 129.1, 126.8, 122.9, 117.0, 115.5, 50.7, 39.4, 32.4, 30.1, 25.8, 19.4, 13.5, 8.9; HRMS (ESI) calcd for C20H26ClNNaO3S (M + Na)+ 418.1214, found 418.1218. Compound 3e. 67 mg, 76% yield, colorless oil; 1H NMR (600 MHz, CDCl3) δ 7.53−7.51 (m, 2H), 7.37−7.35 (m, 2H), 5.87−5.80 (m, 1H), 5.06 (dd, J = 17.1, 1.7 Hz, 1H), 5.01 (dd, J = 10.2, 1.7 Hz, 1H), 3.39 (t, J = 7.2 Hz, 2H), 3.04 (s, 3H), 2.69 (t, J = 7.5 Hz, 2H), 2.40−2.36 (m, 2H), 1.91 (s, 3H), 1.25−1.20 (m, 2H), 1.13−1.06 (m, 2H), 0.70 (t, J = 7.4 Hz, 3H); 13C NMR (151 MHz, CDCl3) δ 149.0, 138.7, 137.2, 131.5, 130.8, 130.7, 123.6, 121.5, 115.5, 115.1, 50.8, 39.4, 32.4, 30.2, 25.7, 19.5, 13.5, 9.2; HRMS (ESI) calcd for C20H26BrNNaO3S (M + Na)+ 462.0709, found 462.0706. Compound 3f. 60 mg, 80% yield, colorless oil; 1H NMR (600 MHz, CDCl3) δ 7.34 (d, J = 8.0 Hz, 2H), 7.19 (d, J = 7.9 Hz, 2H), 5.88−5.81 (m, 1H), 5.06 (dd, J = 17.1, 1.4 Hz, 1H), 5.01 (d, J = 10.2 Hz, 1H), 3.40 (t, J = 7.2 Hz, 2H), 2.97 (s, 3H), 2.69 (t, J = 7.5 Hz, 2H), 2.42−2.36 (m, 2H), 2.36 (s, 3H), 1.91 (s, 3H), 1.31−1.26 (m, 2H), 1.15−1.09 (m, 2H), 0.71 (t, J = 7.4 Hz, 3H); 13C NMR (151 MHz, CDCl3) δ 148.6, 138.6, 137.4, 136.9, 129.0, 128.8, 124.3, 115.4,

a Reaction conditions: 1a (0.2 mmol), 2 (0.4 mmol), PdBr2 (10 mol %), DDQ (0.04 mmol), MnO2 (0.6 mmol), MeCN (2 mL), under N2, 50 °C, 12 h with isolated yields. bE/Z or Z/E = 2.6:1. c3.5 h.

Scheme 4. Proposed Mechanism

complementary protocol to traditional allylation methods23 because of the excellent γ-selectivity.

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EXPERIMENTAL SECTION

General. Melting points reported here were measured by a melting point instrument and were uncorrected. 1H, 13C, and 19F NMR spectra were measured on a 600 or 400 MHz NMR spectrometers with CDCl3 as the solvent using tetramethylsilane (TMS) as the internal standard. Chemical shifts were given in δ relative to TMS, and the coupling constants were given in Hz. High-resolution mass spectra (HRMS) 11137

DOI: 10.1021/acs.joc.7b02131 J. Org. Chem. 2017, 82, 11134−11140

Article

The Journal of Organic Chemistry

10.2, 1.4 Hz, 1H), 3.07 (s, 3H), 2.76 (t, J = 7.5 Hz, 2H), 2.49−2.43 (m, 2H), 1.92 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 149.1, 140.4, 139.4, 137.3, 131.5, 129.27, 129.0, 128.2, 127.5, 127.3, 126.5, 123.7, 115.6, 115.5, 39.6, 32.4, 25.8, 9.2; HRMS (ESI) calcd for C22H23NNaO3S (M + Na)+ 404.1291, found 404.1291. Crystal data for 3n (C22H23NO3S, 381.48): triclinic, space group P1̅ a = 10.7119(7) Å, b = 12.3681(7) Å, c = 15.6167(10) Å, V = 2009.3(2) Å3, Z = 2, T = 296(2) K, absorption coefficient 0.182 mm−1, reflections collected 57443, independent reflections 6896 [R(int) = 0.0821], refinement by full-matrix least-squares on F2, data/restraints/parameters 6896/0/ 487, goodness-of-fit on F2 = 1.628, final R indices [I > 2s(I)] R1 = 0.1264, wR2 = 0.2487, R indices (all data) R1 = 0.1620, wR2 = 0.2604, largest diff peak and hole 0.378 and −0.323 e.Å−3. Crystallographic data for the structure of 3n have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC 1569891. Compound 3o. 65 mg, 82% yield, colorless oil; 1H NMR (600 MHz, CDCl3) δ 7.29−7.25 (m, 3H), 7.22−7.19 (m, 1H), 7.16−7.11 (m, 4H), 7.03 (d, J = 7.3 Hz, 2H), 5.86−5.79 (m, 1H), 5.07 (dd, J = 17.1, 1.7 Hz, 1H), 5.02 (dd, J = 10.2, 1.5 Hz, 1H), 4.55 (s, 2H), 2.95 (s, 3H), 2.66 (t, J = 7.4 Hz, 2H), 2.38−2.34 (m, 2H), 1.83 (s, 3H); 13C NMR (151 MHz, CDCl3) δ 148.6, 138.6, 137.3, 134.9, 131.4, 129.1, 129.0, 128.2, 128.1, 127.9, 127.1, 124.4, 115.4, 115.4, 55.0, 40.4, 32.4, 25.7, 9.1; HRMS (ESI) calcd for C23H25NNaO3S (M + Na)+ 418.1447, found 418.1431. Compound 3p. 51 mg, 66% yield, colorless oil; 1H NMR (600 MHz, CDCl3) δ 7.53−7.51 (m, 2H), 7.42−7.39 (m, 2H), 7.34−7.29 (m, 1H), 5.92−5.85 (m, 1H), 5.07 (dd, J = 17.1, 1.7 Hz, 1H), 5.01 (dd, J = 10.2, 1.6 Hz, 1H), 3.74−3.69 (m, 1H), 3.11 (d, J = 3.1 Hz, 3H), 2.72 (t, J = 7.5 Hz, 2H), 2.44−2.40 (m, 2H), 1.96 (s, 3H), 1.64 (s, 2H), 1.51 (d, J = 13.1 Hz, 1H), 1.31−1.19 (m, 3H), 1.01−0.84 (m, 4H); 13C NMR (151 MHz, CDCl3) δ 148.7, 137.3, 137.0, 132.2, 129.3, 128.1, 127.2, 125.7, 115.4, 115.3, 61.1, 41.4, 32.4, 32.3, 25.7, 25.7, 24.9, 9.3; HRMS (ESI) calcd for C22H29NNaO3S (M + Na)+ 410.1760, found 410.1762. Compound 3q. 59 mg, 70% yield, colorless oil; 1H NMR (600 MHz, CDCl3) δ 7.28−7.21 (m, 8H), 7.10−7.08 (m, 2H), 5.85−5.78 (m, 1H), 5.04 (dd, J = 17.1, 1.6 Hz, 1H), 4.99 (dd, J = 10.2, 1.2 Hz, 1H), 3.47 (t, J = 7.2 Hz, 2H), 3.02 (s, 3H), 2.80−2.77 (m, 2H), 2.44− 2.41 (m, 2H), 1.34−1.29 (m, 2H), 1.16−1.10 (m, 2H), 0.70 (t, J = 7.4 Hz, 3H); 13C NMR (151 MHz, CDCl3) δ 149.5, 139.6, 137.1, 132.4, 131.0, 129.8, 129.5, 128.2, 128.0, 127.2, 126.8, 123.5, 122.7, 115.6, 51.2, 39.7, 32.4, 30.4, 26.1, 19.6, 13.5; HRMS (ESI) calcd for C25H29NNaO3S (M + Na)+ 446.1760, found 446.1759. Compound 3r. 77 mg, 90% yield, colorless oil; 1H NMR (600 MHz, CDCl3) δ 7.38−7.34 (m, 4H), 7.33−7.29 (m, 1H), 5.87 (m, 1H), 5.08 (dd, J = 17.1, 1.7 Hz, 1H), 5.01 (dd, J = 10.2, 1.5 Hz, 1H), 3.36 (t, J = 7.1 Hz, 2H), 2.91 (s, 3H), 2.78−2.74 (m, 2H), 2.41 (m, 2H), 2.33 (m, 1H), 1.70 (t, J = 15.1 Hz, 4H), 1.62 (s, 1H), 1.41−1.34 (m, 2H), 1.30−1.26 (m, 2H), 1.17 (m, 2H), 1.11−1.05 (m, 3H), 0.72 (t, J = 7.4 Hz, 3H); 13C NMR (151 MHz, CDCl3) δ 147.9, 138.6, 137.4, 132.35, 130.1, 128.0, 127.3, 125.4, 124.3, 115.3, 50.9, 39.4, 35.2, 33.2, 32.9, 30.4, 27.0, 26.9, 26.0, 19.5, 13.5; HRMS (ESI) calcd for C25H35NNaO3S (M + Na)+ 452.2230, found 452.2227. Compound 3s. 29 mg, 40% yield, colorless oil; 1H NMR (600 MHz, CDCl3) δ 7.69−7.67 (m, 2H), 7.38−7.35 (m, 2H), 7.27 (d, J = 6.8 Hz, 1H), 6.29 (d, J = 0.8 Hz, 1H), 5.80−5.73 (m, 1H), 5.07−5.03 (m, 2H), 3.54−3.52 (m, 2H), 3.06 (s, 3H), 2.92−2.86 (m, 1H), 2.48− 2.43 (m, 1H), 2.32−2.28 (m, 1H), 1.40−1.35 (m, 2H), 1.27 (d, J = 7.0 Hz, 3H), 1.23−1.19 (m, 2H), 0.74 (t, J = 7.4 Hz, 3H); 13C NMR (151 MHz, CDCl3) δ 157.6, 138.5, 135.8, 131.5, 128.5, 127.4, 127.1, 122.8, 116.8, 105.8, 51.0, 39.8, 39.5, 33.0, 30.3, 19.7, 18.0, 13.5; HRMS (ESI) calcd for C20H27NNaO3S (M + Na)+ 384.1604, found 384.1604. Compound 3u. 59 mg, 79% yield, colorless oil; 1H NMR (600 MHz, CDCl3) δ 7.46 (d, J = 7.6 Hz, 2H), 7.38 (t, J = 7.6 Hz, 2H), 7.30 (t, J = 7.4 Hz, 1H), 4.75 (s, 1H), 4.71 (s, 1H), 3.40 (t, J = 7.1 Hz, 2H), 2.99 (s, 3H), 2.76−2.73 (m, 2H), 2.34 (t, J = 7.7 Hz, 2H), 1.93 (s, 3H), 1.77 (s, 3H), 1.29−1.24 (m, 2H), 1.12−1.06 (m, 2H), 0.69 (t, J = 7.4 Hz, 3H); 13C NMR (151 MHz, CDCl3) δ 148.9, 144.6, 138.6, 131.8, 129.1, 128.3, 127.3, 124.5, 115.2, 110.7, 50.9, 39.5, 36.2, 30.3,

50.9, 39.6, 32.4, 30.4, 25.8, 21.2, 19.6, 13.5, 9.2; HRMS (ESI) calcd for C21H29NNaO3S (M + Na)+ 398.1760, found 398.1760. Compound 3g. 57 mg, 73% yield, 1H NMR (600 MHz, CDCl3) δ 7.29 (t, J = 7.9 Hz, 1H), 7.13−7.12 (m, 1H), 7.01 (d, J = 7.6 Hz, 1H), 6.87−6.85 (m, 1H), 5.88−5.81 (m, 1H), 5.07 (dd, J = 17.1, 1.6 Hz, 1H), 5.01 (dd, J = 10.2, 1.2 Hz, 1H), 3.83 (s, 3H), 3.40 (t, J = 7.1 Hz, 2H), 3.01 (s, 3H), 2.69 (t, J = 7.5 Hz, 2H), 2.40−2.37 (m, 2H), 1.94 (s, 3H), 1.29−1.24 (m, 2H), 1.14−1.07 (m, 2H), 0.70 (t, J = 7.4 Hz, 3H); 13C NMR (151 MHz, CDCl3) δ 159.5, 148.7, 138.7, 137.3, 133.0, 129.2, 124.4, 121.4, 115.4, 115.3, 114.3, 113.5, 55.3, 50.9, 39.6, 32.4, 30.3, 25.7, 19.5, 13.5, 9.2; HRMS (ESI) calcd for C21H29NNaO4S (M + Na)+ 414.1710, found 414.1712. Compound 3h. 62 mg, 76% yield, colorless oil; 1H NMR (600 MHz, CDCl3) δ 8.27−8.25 (m, 2H), 7.70 (d, J = 8.8 Hz, 2H), 5.87− 5.80 (m, 1H), 5.07 (dd, J = 17.1, 1.6 Hz, 1H), 5.02 (dd, J = 10.2, 1.3 Hz, 1H), 3.42 (t, J = 7.2 Hz, 2H), 3.09 (s, 3H), 2.72 (t, J = 7.4 Hz, 2H), 2.42−2.38 (m, 2H), 1.96 (s, 3H), 1.26−1.19 (m, 2H), 1.11−1.05 (m, 2H), 0.69 (t, J = 7.4 Hz, 3H); 13C NMR (151 MHz, CDCl3) δ 149.6, 147.0, 139.5, 138.8, 136.9, 129.9, 123.5, 123.0, 115.7, 114.9, 50.8, 39.2, 32.3, 30.1, 25.6, 19.4, 13.4, 9.2; HRMS (ESI) calcd for C20H26N2NaO5S (M + Na)+ 429.1455, found 429.1454. Compound 3i. 67 mg, 80% yield, colorless oil; 1H NMR (600 MHz, CDCl3) δ 8.07 (d, J = 8.3 Hz, 2H), 7.57 (d, J = 8.3 Hz, 2H), 5.88−5.81 (m, 1H), 5.07 (dd, J = 17.1, 1.5 Hz, 1H), 5.02 (dd, J = 10.2, 1.0 Hz, 1H), 3.93 (s, 3H), 3.40 (t, J = 7.2 Hz, 2H), 3.04 (s, 3H), 2.70 (t, J = 7.5 Hz, 2H), 2.39 (m, 2H), 1.94 (s, 3H), 1.26−1.21 (m, 2H), 1.11− 1.05 (m, 2H), 0.68 (t, J = 7.4 Hz, 3H); 13C NMR (151 MHz, CDCl3) δ 167.0, 149.1, 139.1, 137.1, 136.6, 129.6, 129.1, 128.9, 123.8, 115.6, 115.1, 52.1, 50.8, 39.4, 32.3, 30.2, 25.7, 19.5, 13.4, 9.2; HRMS (ESI) calcd for C22H29NNaO5S (M + Na)+ 442.1659, found 442.1660. Compound 3j. 52 mg, 71% yield, colorless oil; 1H NMR (600 MHz, CDCl3) δ 7.31−7.28 (m, 2H), 7.07−7.05 (m, 1H), 5.86−5.79 (m, 1H), 5.05 (dd, J = 17.1, 1.6 Hz, 1H), 5.00 (dd, J = 10.2, 1.3 Hz, 1H), 3.53−3.50 (m, 2H), 3.01 (s, 3H), 2.69 (t, J = 7.5 Hz, 2H), 2.39− 2.36 (m, 2H), 2.07 (s, 3H), 1.43−1.38 (m, 2H), 1.25−1.19 (m, 2H), 0.80 (t, J = 7.4 Hz, 3H); 13C NMR (151 MHz, CDCl3) δ 149.0, 138.6, 137.1, 132.6, 127.0, 126.3, 125.2, 118.2, 115.5, 115.2, 50.8, 39.5, 32.4, 30.4, 25.6, 19.7, 13.6, 9.8; HRMS (ESI) calcd for C18H25NNaO3S2 (M + Na)+ 390.1168, found 390.1165. Compound 3k. 57 mg, 74% yield, colorless oil; 1H NMR (600 MHz, CDCl3) δ 7.46 (d, J = 7.4 Hz, 2H), 7.33 (t, J = 7.7 Hz, 2H), 7.25−7.22 (m, 1H), 7.02 (d, J = 16.8 Hz, 1H), 6.91 (d, J = 16.7 Hz, 1H), 5.84−5.78 (m, 1H), 5.04 (dd, J = 17.1, 1.7 Hz, 1H), 4.99 (dd, J = 10.2, 1.6 Hz, 1H), 3.59−3.56 (m, 2H), 3.03 (s, 3H), 2.66 (t, J = 7.4 Hz, 2H), 2.37−2.33 (m, 2H), 2.14 (s, 3H), 1.50−1.45 (m, 2H), 1.40− 1.33 (m, 2H), 0.87 (t, J = 7.3 Hz, 3H); 13C NMR (151 MHz, CDCl3) δ 149.1, 139.8, 137.7, 137.2, 130.0, 128.6, 127.4, 126.3, 121.0, 118.6, 115.5, 114.5, 50.5, 39.0, 32.5, 30.4, 25.3, 19.7, 13.6, 10.3; HRMS (ESI) calcd for C22H29NNaO3S (M + Na)+ 410.1760, found 410.1760. Compound 3l. 56 mg, 76% yield, colorless oil; 1H NMR (600 MHz, CDCl3) δ 5.76−5.83 (m, 1H), 5.02 (dd, J = 17.1, 1.7 Hz, 1H), 4.97 (dd, J = 10.2, 1.7 Hz, 1H), 3.52−3.49 (m, 2H), 2.96 (s, 3H), 2.60 (t, J = 7.5 Hz, 2H), 2.33−2.29 (m, 4H), 1.89 (s, 3H), 1.49−1.45 (m, 4H), 1.36−1.29 (m, 8H), 0.91−0.91 (m, 6H); 13C NMR (151 MHz, CDCl3) δ 148.1, 137.9, 137.4, 123.9, 115.8, 115.2, 50.2, 38.6, 32.5, 31.6, 30.5, 29.7, 29.2, 25.6, 23.7, 22.6, 19.7, 14.0, 13.6, 8.7; HRMS (ESI) calcd for C20H35NNaO3S (M + Na)+ 392.2230, found 392.2228. Compound 3m. 66 mg, 75% yield, colorless oil; 1H NMR (400 MHz, CDCl3) δ 7.71 (d, J = 8.2 Hz, 2H), 7.47−7.45 (m, 2H), 7.39− 7.35 (m, 2H), 7.32−7.27 (m, 1H), 7.26 (d, J = 7.2 Hz, 2H), 5.87−5.87 (m, 1H), 5.05 (dd, J = 17.1, 1.6 Hz, 1H), 5.00 (d, J = 10.2 Hz, 1H), 3.24 (t, J = 7.1 Hz, 2H), 2.62 (t, J = 7.5 Hz, 2H), 2.43 (s, 3H), 2.33− 2.28 (m, 2H), 1.92 (s, 3H), 1.19−1.13 (m, 2H), 1.05−1.00 (m, 2H), 0.64 (t, J = 7.3 Hz, 3H); 13C NMR (151 MHz, CDCl3) δ 148.4, 143.4, 138.6, 137.4, 136.5, 131.9, 129.3, 129.2, 128.1, 127.1, 124.9, 115.3, 115.1, 50.3, 32.3, 29.9, 25.7, 21.5, 19.5, 13.5, 9.2; HRMS (ESI) calcd for C26H31NNaO3S (M + Na)+ 460.1917, found 460.1910. Compound 3n. 55 mg, 72% yield, white solid, mp: 121−123 °C; 1 H NMR (400 MHz, CDCl3) δ 7.38−7.31 (m, 7H), 7.30−7.26 (m, 3H), 5.95−5.85 (m, 1H), 5.11 (dd, J = 17.1, 1.6 Hz, 1H), 5.04 (dd, J = 11138

DOI: 10.1021/acs.joc.7b02131 J. Org. Chem. 2017, 82, 11134−11140

Article

The Journal of Organic Chemistry

Compound 3ac. 32 mg, 40% yield, colorless oil; 1H NMR (600 MHz, CDCl3) δ 7.50 (d, J = 7.2 Hz, 2H), 7.41 (t, J = 7.6 Hz, 2H), 7.33 (t, J = 7.4 Hz, 1H), 5.77−5.74 (m, 1H), 5.62−5.60 (m, 1H), 3.43 (t, J = 7.1 Hz, 2H), 3.02 (s, 3H), 2.66−2.56 (m, 2H), 2.52−2.49 (m, 1H), 2.04−2.02 (m, 2H), 1.96 (s, 3H), 1.83−1.75 (m, 2H), 1.62−1.54 (m, 2H), 1.31−1.28 (m, 2H), 1.16−1.10 (m, 2H), 0.72 (t, J = 7.3 Hz, 3H); 13 C NMR (151 MHz, CDCl3) δ 148.3, 138.7, 131.8, 130.6, 129.2, 128.3, 127.9, 127.3, 124.4, 116.1, 50.9, 39.5, 35.1, 32.6, 30.3, 28.8, 25.2, 21.2, 19.6, 13.5, 9.3; HRMS (ESI) calcd for C23H31NNaO3S (M + Na)+ 424.1917, found 424.1906. Compound 3ad. 68 mg, 78% yield, colorless oil; 1H NMR (600 MHz, CDCl3) δ 7.46−7.44(m, 2H), 7.40−7.37 (m, 2H), 7.32−7.30 (m, 1H), 5.09 (d, J = 0.7 Hz, 1H), 4.98 (d, J = 0.7 Hz, 1H), 4.57 (s, 2H), 3.40 (t, J = 7.2 Hz, 2H), 2.97 (s, 3H), 2.79−2.77 (m, 2H), 2.41 (t, J = 7.6 Hz, 2H), 2.11 (s, 3H), 1.93 (s, 3H), 1.28−1.24 (m, 2H), 1.13−1.07 (m, 2H), 0.69 (t, J = 7.4 Hz, 3H); 13C NMR (151 MHz, CDCl3) δ 170.6, 148.2, 142.6, 138.8, 131.6, 129.1, 128.3, 127.3, 124.5, 115.5, 113.3, 66.6, 50.9, 39.5, 31.7, 30.3, 24.6, 20.9, 19.5, 13.5, 9.1; HRMS (ESI) calcd for C23H31NNaO5S (M + Na)+ 456.1815, found 456.1805. Compound 3ae. 56 mg, 71% yield, colorless oil; 1H NMR (600 MHz, CDCl3) δ 7.44 (d, J = 7.3 Hz, 2H), 7.38 (t, J = 7.6 Hz, 2H), 7.31 (t, J = 7.3 Hz, 1H), 5.08 (s, 1H), 4.92 (s, 1H), 4.05 (s, 2H), 3.39 (t, J = 7.1 Hz, 2H), 2.98 (s, 3H), 2.78 (t, J = 7.5 Hz, 2H), 2.41 (t, J = 7.5 Hz, 2H), 1.93 (s, 3H), 1.27−1.25 (m, 2H), 1.12−1.06 (m, 2H), 0.69 (t, J = 7.4 Hz, 3H); 13C NMR (151 MHz, CDCl3) δ 148.6, 147.8, 138.7, 131.6, 129.1, 128.3, 127.3, 124.4, 115.4, 110.5, 65.7, 50.9, 39.6, 31.2, 30.3, 25.0, 19.5, 13.5, 9.1; HRMS (ESI) calcd for C21H29NNaO4S (M + Na)+ 414.1710, found 414.1705.

24.7, 22.3, 19.5, 13.5, 9.2; HRMS (ESI) calcd for C21H29NNaO3S (M + Na)+ 398.1760, found 398.1747. Compound 3v. 74 mg, 85% yield, colorless oil; 1H NMR (600 MHz, CDCl3) δ 7.46−7.29 (m, 10H), 5.33 (d, J = 0.8 Hz, 1H), 5.09 (d, J = 1.02 Hz, 1H), 3.41 (t, J = 7.1 Hz, 2H), 2.99 (s, 3H), 2.87 (t, J = 7.5 Hz, 2H), 2.77 (t, J = 7.5 Hz, 2H), 1.80 (s, 3H), 1.30−1.25 (m, 2H), 1.14−1.08 (m, 2H), 0.70 (t, J = 7.4 Hz, 3H); 13C NMR (151 MHz, CDCl3) δ 148.5, 147.2, 140.6, 138.7, 131.7, 129.1, 128.4, 128.3, 127.5, 127.3, 126.1, 124.4, 115.6, 113.1, 51.0, 39.5, 33.9, 30.4, 25.2, 19.5, 13.5, 9.1; HRMS (ESI) calcd for C26H31NNaO3S (M + Na)+ 460.1917, found 460.1901. Compound 3w. 72 mg, 78% yield, colorless oil; 1H NMR (600 MHz, CDCl3) δ 7.50−7.48 (m, 2H), 7.42−7.40 (m, 2H), 7.34−7.32 (m, 1H), 5.67−5.61 (m, 1H), 5.08 (dd, J = 17.1, 1.7 Hz, 1H), 5.01 (dd, J = 10.2, 1.5 Hz, 1H), 3.42 (t, J = 7.2 Hz, 2H), 3.02 (s, 3H), 2.69− 2.59 (m, 2H), 2.42−2.36 (m, 1H), 1.94 (s, 3H), 1.35−1.26 (m, 14H), 1.15−1.10 (m, 2H), 0.90 (t, J = 7.0 Hz, 3H), 0.72 (t, J = 7.4 Hz, 3H); 13 C NMR (151 MHz, CDCl3) δ 148.2, 142.0, 138.6, 131.8, 129.2, 128.3, 127.2, 124.4, 116.0, 114.7, 50.9, 43.6, 39.4, 34.3, 32.0, 31.9, 30.3, 29.7, 29.3, 27.1, 22.7, 19.6, 14.1, 13.5, 9.4; HRMS (ESI) calcd for C27H41NNaO3S (M + Na)+ 482.2699, found 482.2691. Compound 3x. 66 mg, 88% yield, colorless oil; 1H NMR (600 MHz, CDCl3) δ 7.46 (d, J = 7.1 Hz, 2H), 7.38 (t, J = 7.7 Hz, 2H), 7.30 (t, J = 7.4 Hz, 1H), 5.82−5.77 (m, 1H), 5.03 (d, J = 17.2 Hz, 1H), 4.98 (d, J = 10.4 Hz, 1H), 3.40 (t, J = 7.1 Hz, 2H), 2.98 (s, 3H), 2.66−2.62 (m, 1H), 2.58−2.53 (m, 2H), 1.92 (s, 3H), 1.29−1.24 (m, 2H), 1.13− 1.08 (m, 2H), 1.06 (d, J = 6.3 Hz, 3H), 0.69 (t, J = 7.4 Hz, 3H); 13C NMR (151 MHz, CDCl3) δ 148.0, 143.1, 138.7, 131.7, 129.1, 128.2, 127.2, 124.3, 116.1, 113.1, 50.9, 39.5, 37.3, 33.3, 30.3, 19.6, 19.4, 13.5, 9.4; HRMS (ESI) calcd for C21H29NNaO3S (M + Na)+ 398.1760, found 398.1750. Compound 3y. 53 mg, 70% yield, colorless oil; E/Z or Z/E = 2.6:1; 1 H NMR (600 MHz, CDCl3) δ 7.47−7.46 (m, 2H), 7.40−7.38 (m, 2H), 7.32−7.29 (m, 1H), 5.54−5.47 (m, 1H), 5.45−5.40 (m, 1H), 3.40 (t, J = 7.1 Hz, 2H), 3.00 (s, 3H), 2.38 (q, J = 7.3 Hz, 1.5H), 2.32− 2.29 (m, 0.6H), 1.93 (s, 2.10H), 1.92 (s, 0.80H), 1.66 (d, J = 4.9 Hz, 0.8H), 1.60−1.59 (m, 1.1H), 1.58−1.57 (m, 1.0H), 1.28−1.23 (m, 2H), 1.12−1.06 (m, 2H), 0.70−0.67 (m, 3H); 13C NMR (151 MHz, CDCl3) δ 149.0, 138.6, 131.8, 129.1, 128.8, 128.3, 127.3, 125.1, 124.5, 115.3, 51.0, 39.5, 30.3, 26.0, 25.7, 19.5, 17.9, 13.5, 9.2; HRMS (ESI) calcd for C21H29NNaO3S (M + Na)+ 398.1760, found 398.1750. Compound 3z. 49 mg, 55% yield, colorless oil; 1H NMR (600 MHz, CDCl3) δ 7.47−7.45 (m, 2H), 7.40−7.37 (m, 2H), 7.32−7.29 (m, 1H), 5.42−5.35 (m, 2H), 3.40 (t, J = 7.1 Hz, 2H), 3.00 (s, 3H), 2.64 (t, J = 7.5 Hz, 2H), 2.32−2.29 (m, 2H), 1.91 (s, 3H), 1.91−1.88 (m, 1H), 1.72−1.62 (m, 4H), 1.29−1.21 (m, 4H), 1.16−1.08 (m, 4H), 1.06−1.02 m, 2H), 0.69 (t, J = 7.4 Hz, 3H); 13C NMR (151 MHz, CDCl3) δ 149.0, 138.6, 137.8, 131.8, 129.1, 128.3, 127.3, 125.9, 124.4, 115.3, 51.0, 40.6, 39.5, 33.1, 31.4, 30.4, 26.6, 26.2, 26.0, 19.5, 13.5, 9.2; HRMS (ESI) calcd for C26H37NNaO3S (M + Na)+ 466.2386, found 466.2383. Compound 3aa. 72 mg, 93% yield, colorless oil; 1H NMR (600 MHz, CDCl3) δ 7.49−7.46 (m, 2H), 7.40−7.37 (m, 2H), 7.31−7.29 (m, 1H), 5.92−5.88 (m, 1H), 4.95 (dd, J = 17.5, 1.1 Hz, 1H), 4.92 (dd, J = 10.7, 1.1 Hz, 1H), 3.39 (t, J = 7.1 Hz, 2H), 3.00 (s, 3H), 2.58 (s, 2H), 1.92 (s, 3H), 1.28−1.23 (m, 2H), 1.12−1.06 (m, 8H), 0.69 (t, J = 7.4 Hz, 3H); 13C NMR (151 MHz, CDCl3) δ 147.7, 147.5, 138.9, 131.9, 129.2, 128.3, 127.3, 124.3, 117.2, 110.6, 50.9, 39.4, 39.1, 38.4, 30.3, 26.7, 19.6, 13.5, 9.9; HRMS (ESI) calcd for C22H31NNaO3S (M + Na)+ 412.1917, found 412.1919. Compound 3ab. 77 mg, 95% yield, colorless oil; 1H NMR (600 MHz, CDCl3) δ 7.50−7.49 (m, 2H), 7.42−7.40 (m, 2H), 7.34−7.31 (m, 1H), 4.78−4.77 (m, 1H), 4.70−4.69 (m, 1H), 3.44−3.41 (m, 2H), 3.02 (s, 3H), 2.68−2.67 (m, 2H), 2.39−2.34 (m, 1H), 1.95 (s, 3H), 1.69 (s, 3H), 1.53−1.40 (m, 2H), 1.31−1.26 (m, 2H), 1.15−1.09 (m, 2H), 0.88 (t, J = 7.4 Hz, 3H), 0.72 (t, J = 7.4 Hz, 3H); 13C NMR (151 MHz, CDCl3) δ 148.4, 146.3, 138.4, 131.7, 129.1, 128.2, 127.2, 124.3, 115.6, 111.9, 50.8, 48.3, 39.3, 30.7, 30.1, 25.4, 19.5, 18.5, 13.4, 11.8, 9.2; HRMS (ESI) calcd for C23H33NNaO3S (M + Na)+ 426.2073, found 426.2062.

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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.7b02131. Spectroscopic data of products 3 (PDF) Crystallographic data of 3n(CIF)

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AUTHOR INFORMATION

Corresponding Authors

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

Yan Zhang: 0000-0002-0694-5131 Gangguo Zhu: 0000-0003-4384-824X Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work is supported by the National Natural Science Foundation of China (21672191), Science Technology Department of Zhejiang Province, China (2015C31030), Natural Science Foundation of Zhejiang Province (LY18B020008), and Key Laboratory of the Ministry of Education for Advanced Catalysis Materials.

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REFERENCES

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