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Synlett 2018; 29(12): 1654-1658
DOI: 10.1055/s-0037-1610145
DOI: 10.1055/s-0037-1610145
letter
Iodine-Mediated Vicinal Difunctionalization of Alkenes: A Convenient Method for Building C–Se and C–S Bonds
Further Information
Publication History
Received: 06 March 2018
Accepted after revision: 22 April 2018
Publication Date:
30 May 2018 (online)
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.
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- 15 Difunctionalizations of Alkenes Mediated by I2; Typical Procedure In a mixed solvent H2O/EtOH (1:1, 3.0 mL), alkene 1 (0.24 mmol), diselenide 2 (0.10 mmol), sodium dithiocarbamate 3 (0.6 mmol) and I2 (0.1 mmol) were added successively. The suspension mixture was vigorously stirred at r.t. for 6 h. Upon completion, the reaction was quenched by addition of sat. aq. Na2S2O3 (2 mL) and H2O (5 mL). 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.