Synlett, Table of Contents Synlett 2018; 29(12): 1654-1658DOI: 10.1055/s-0037-1610145 letter © Georg Thieme Verlag Stuttgart · New York Iodine-Mediated Vicinal Difunctionalization of Alkenes: A Convenient Method for Building C–Se and C–S Bonds Junxing Wang College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, P. R. of China Email: jieyan87@zjut.edu.cn , Weijian Sheng College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, P. R. of China Email: jieyan87@zjut.edu.cn , Jie Yan* College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, P. R. of China Email: jieyan87@zjut.edu.cn › Author Affiliations Recommend Article Abstract Buy Article All articles of this category Abstract A novel I2-mediated procedure is developed for building C–Se and C–S bonds simultaneously from alkenes, diselenides and sodium dithiocarbamates. This difunctionalization of alkenes is carried out in the presence of I2 and air, and exhibits good characteristics such as being transition-metal-free, requiring mild reaction conditions and simple procedures. The approach provides the product β-selanylethyl dithiocarbamates with high regioselectivity and in good yields. A plausible electrophilic addition mechanism is hypothesized. Key words Key wordsdifunctionalization of alkene - β-selanylethyl dithiocarbamate - alkene - diselenide - iodine-mediated Full Text References References and Notes 1a Wirth T. Tetrahedron 1999; 55: 1 1b Wirth T. Angew. Chem. Int. Ed. 2000; 39: 3740 1c Freudendahl DM. Shahzad SA. Wirth T. Eur. J. Org. Chem. 2009; 1649 1d Mukherjee AJ. Zade SS. Singh HB. Sunoj RB. Chem. Rev. 2010; 110: 4357 1e Letavayova L. Vlckova V. Brozmanova J. Toxicology 2006; 227: 1 1f Erkekoglu P. Rachidi W. Yuzugullu OG. Giray B. Favier A. Ozturk M. Hincal F. Toxicol. Appl. Pharmacol. 2010; 248: 52 1g Zeni G. Stracke MP. Nogueira CW. 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The mixture was extracted with CH2Cl2 (3 × 5 mL) and the combined organic phase was dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The residue was then purified on a silica gel plate (PE/EtOAc, 6:1) to furnish product 4. 1-Phenyl-2-phenylselanyletheyl Diethylcarbamodithioate (4a): Yield: 74 mg (91%); yellow oil. IR (film): 3057, 2979, 2931, 1485, 1418, 1268, 1206, 736, 694 cm–1. 1H NMR (500 MHz, CDCl3): δ = 7.52 (d, J = 3.7 Hz, 2 H), 7.37–7.32 (m, 6 H), 7.25–7.22 (m, 2 H), 5.37 (d, J = 6.3 Hz, 1 H), 4.13–3.92 (m, 2 H), 3.92 (dd, J = 11.9, 4.8 Hz, 1 H), 3.72–3.67 (m, 2 H), 3.48 (dd, J = 11.9, 11.0 Hz, 1 H), 1.30–1.20 (m, 6 H). 13C NMR (125 MHz, CDCl3): δ = 193.6, 138.8, 133.6, 130.0, 128.9, 128.6, 128.0, 127.1, 55.7, 49.3, 46.7, 33.5, 12.6, 11.6. MS (ESI): m/z = 432 [M+23]+. HRMS: m/z [M+23]+ calcd for C19H23NNaS2Se: 432.0335; found: 432.0321. 2-(Phenylselanyl)-1-(p-tolyl)ethyl Diethylcarbamodithioate (4b): Yield: 72 mg (85%); yellow oil. IR (film): 3052, 2976, 2931, 1487, 1417, 1268, 1206, 827, 737, 691 cm–1. 1H NMR (500 MHz, CDCl3): δ = 7.56–7.53 (m, 2 H), 7.29–7.22 (m, 5 H), 7.15 (d, J = 5.0 Hz, 2 H), 5.32 (dd, J = 11.2, 4.7 Hz, 1 H), 4.05–3.94 (m, 2 H), 3.93 (dd, J = 11.8, 4.7 Hz, 1 H), 3.72–3.67 (m, 2 H), 3.49 (d, J = 11.5 Hz, 1 H), 2.36 (s, 3 H), 1.29–1.23 (m, 6 H). 13C NMR (125 MHz, CDCl3): δ = 193.7, 137.7, 135.6, 133.6, 129.3, 129.2, 128.8, 128.4, 127.0, 55.3, 49.2, 46.6, 33.4, 21.2, 12.6, 11.6. MS (ESI): m/z = 446 [M+23]+; HRMS (ESI): m/z [M+23]+ calcd for C20H25NNaS2Se: 446.0491; found: 446.0478. 1-(4-Chlorophenyl)-2-phenylselanyletheyl Diethylcarbamodithioate (4d): Yield: 149 mg (55%); yellow oil. IR (film): 3054, 2956, 2920, 2849, 1486, 1416, 1269, 1205, 1091, 1011, 829, 735, 690 cm–1. 1H NMR (500 MHz, CDCl3): δ = 7.51–7.47 (m, 2 H), 7.29–7.22 (m, 7 H), 5.36–5.30 (m, 1 H), 4.10–3.94 (m, 2 H), 3.87 (dd, J = 10.0, 5.0 Hz, 1 H), 3.71–3.62 (m, 2 H), 3.40 (dd, J = 12.1, 11.0 Hz, 1 H), 1.28–1.23 (m, 6 H). 13C NMR (125 MHz, CDCl3): δ = 193.1, 137.5, 133.7, 130.0, 128.9, 128.7, 127.2, 55.0, 49.4, 46.7, 33.3, 12.6, 11.6; MS (ESI): m/z = 444 [M+1]+; HRMS (ESI): m/z [M+1]+ calcd for C19H23ClNS2Se: 444.0126; found: 444.0098. 1-[2-(Phenylselanyl)indanyl] Diethylcarbamodithioate (4g): Yield: 61 mg (73%); yellow oil. IR (film): 3069, 2973, 2920, 2849, 1485, 1416, 1268, 1205, 909, 732, 690 cm–1. 1H NMR (500 MHz, CDCl3): δ = 7.64–7.60 (m, 2 H), 7.42 (t, J = 5.0 Hz, 1 H), 7.32–7.22 (m, 5 H), 7.19 (d, J = 5.0 Hz, 1 H), 5.60 (d, J = 5.0 Hz, 1 H), 4.30–4.24 (m, 1 H), 4.10–4.00 (m, 2 H), 3.70–3.65 (m, 2 H), 3.56 (dd, J = 16.8, 6.5 Hz, 1 H), 3.05 (dd, J = 16.8, 3.1 Hz, 1 H), 1.34–1.30 (m, 6 H). 13C NMR (125 MHz, CDCl3): δ = 194.6, 143.0, 139.7, 135.8, 131.5, 128.8, 128.4, 127.8, 127.2, 125.8, 124.9, 61.4, 49.3, 47.9, 46.9, 38.6, 12.6, 11.7. MS (ESI): m/z = 422 [M+1]+. HRMS (ESI): m/z [M+1]+ calcd for C20H24NS2Se: 422.0515; found: 422.0511. 16a Muangkaew C. Katrun P. Kanchanarugee P. Pohmakotr M. Reutrakul V. Soorukram D. Jaipetch T. Kuhakarn C. Tetrahedron 2013; 69: 8847 16b Huang Z.-Z. Huang X. Huang Y.-Z. J. Chem. Soc., Perkin Trans. 1 1995; 95 16c Toshimitsu A. Uemura S. Okano M. J. Chem. Soc., Chem. Commun. 1982; 87
