Electrochemical Generation and Catalytic Use of Selenium Electrophiles

Abstract

The generation and use of selenium electrophiles in ­catalytic, electrochemically driven selenenylation-elimination sequences is described.

Key words

electrochemistry - electrophilic addition - elimination - selenium - stereoselective synthesis

References and Notes

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• Diselenides 8 were synthesized according to literature procedures:
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• 15c

  For compound 8d see ref. 5e.

• 16 Prepared by reaction of phenyl acetaldehyde and cyanoacetic acid. Spectroscopic data: Tsuji Y. Yamada N. Tanaka S. J. Org. Chem.  1993,  58:  16 
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10

Typical Experimental Procedure.
The alkene (0.1 mmol) was dissolved in MeOH (7 mL) and tetraethylammonium bromide (0.1 mmol), diselenide (0.01 mmol) and H₂SO₄ (1 µL) were added. The electrodes were inserted into the reaction mixture and constant current of 3 mA applied. After 6 h, electrolysis was stopped and the MeOH removed in vacuo. The mixture was dissolved in Et₂O, washed with NaHCO₃ solution and H₂O before drying over MgSO₄. The products were purified by preparative TLC or column chromatography.

12

Spectroscopic data for 7a: ¹H NMR (400 MHz, CDCl₃): δ = 3.12 (s, 6 H), 3.65 (s, 3 H), 6.24 (d, J = 15.7 Hz, 1 H), 6.73 (d, J = 15.7 Hz, 1 H), 7.20-7.28 (m, 3 H), 7.38-7.40 (m, 2 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 49.7, 51.7, 100.9, 122.0, 126.9, 128.31, 128.33, 139.0, 147.8, 166.7 ppm. IR (NaCl): ν = 2950, 2832, 1727, 1659, 1449, 1436, 1304, 1276, 1192, 1167, 1072, 1046, 988, 700 cm^-1. HRMS: m/z calcd for C₁₃H₁₆O₄: 259.0941; found: 259.0941.

13

Spectroscopic data for 3d: ¹H NMR (400 MHz, CDCl₃): δ = 1.07 (d, J = 6.1 Hz, 3 H), 1.13 (d, J = 6.1 Hz, 3 H), 3.57 (sept, J = 6.1 Hz, 1 H), 3.64 (s, 3 H), 4.95 (dd, J = 5.4, 1.4 Hz, 1 H), 6.02 (dd, J = 15.6, 1.4 Hz, 1 H), 6.91 (dd, J = 15.6, 5.4 Hz, 1 H), 7.19-7.30 (m, 5 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 21.8, 22.6, 51.6, 69.5, 77.8, 120.1, 127.3, 128.0, 128.7, 140.0, 148.8, 166.9 ppm. IR (NaCl): ν = 2971, 1725, 1659, 1453, 1435, 1298, 1272, 1167, 1120, 978, 699 cm^-1. HRMS: m/z calcd for C₁₄H₁₈O₃: 252.1594; found: 252.1593.

14

Spectroscopic data for 3e: ¹H NMR (400 MHz, CDCl₃): δ = 2.06 (s, 3 H), 3.67 (s, 3 H), 5.97 (dd, J = 15.7, 1.5 Hz, 1 H), 6.32 (dd, J = 5.0, 1.5 Hz, 1 H), 6.95 (dd, J = 15.7, 5.0 Hz, 1 H), 7.27-7.31 (m, 5 H). ¹³C NMR (100 MHz, CDCl₃): δ = 21.1, 51.8, 74.2, 121.2, 127.4, 128.83, 128.86, 137.1, 144.9, 166.4, 169.7. IR (NaCl): ν = 2952, 2918, 2849, 1738, 1727, 1662, 1436, 1372, 1310, 1279, 1228, 1197, 1171, 1069, 1022, 980, 699 cm^-1. HRMS: m/z calcd for C₁₃H₁₄O₄: 252.1230; found: 252.1229.

18

Spectroscopic data for 7b: ¹H NMR (400 MHz, CDCl₃): δ = 3.11 (s, 6 H), 5.85 (d, J = 16.2 Hz, 1 H), 6.43 (d, J = 16.2 Hz, 1 H), 7.25-7.38 (m, 5 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 49.8, 100.2, 101.4, 116.8, 126.9, 128.6, 128.8, 137.8, 154.0 ppm. IR (NaCl): ν = 2916, 2848, 2228, 1732, 1450, 1261, 1226, 1191, 1159, 1071, 1047, 972, 774, 746, 702 cm^-1. HRMS: m/z calcd for C₁₂H₁₃NO₂: 221.1285; found: 221.1283.