Stereoselective Michael-Aldol Tandem Reaction of Diorganyl Diselenides or Diorganyl Disulfides with Conjugate Alkynones Mediated by Samarium Diiodide

Abstract

Stereoselective Michael addition and Michael-aldol tandem­ reaction of diorganyl diselenides and diorganyl disulfides with conjugate alkynones mediated by samarium diiodide were studied. The reaction temperature was a dominating factor for the stereoselectivity. β-Organylselenoalkenones or β-organylthio­alkenones and γ-organylselenoallylic alcohols or γ-organylthio­allylic alcohols were prepared in good yields.

Key words

stereoselectivity - Michael-aldol tandem reaction - diorgany­l diselenides - diorganyl disulfide - conjugate alkynones

References

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15

The Michael-aldol tandem reaction products (Z)-2 and (E)-3 were obtained in good yields. All of the products obtained in this study were new and were fully characterized by ¹H NMR, ¹³C NMR, MS, IR, EA spectroscopic methods.
The Representative Procedure of Michael-Aldol Tandem Reaction (Examples: Preparations of 2b and 3b): The reaction was carried out by adding dibutyl disulfides (0.5 mmol) to SmI₂ (1.1 mmol) in THF and the mixture was stirred continuously for 2 h at 60 °C. The tolylphenylacetylenic ketone (1 mmol) and isobutyraldehyde (1 mmol) were added in one portion and were reacted at r.t. or -28 °C. After the reaction was complete checked by TLC. Then 0.1 M HCl was added. The reaction mixture was extracted with Et₂O (3 × 20 mL), and the mixed organic layer was washed with sat. Na₂S₂O₃ solution (10 mL) and H₂O (10 mL). The combined extracts were dried over anhyd Na₂SO₄. After the solvent was removed by evaporation under reduced pressure, the crude product was purified by preparative TLC on silica gel (eluent: cyclohexane/EtOAc = 8:1). Compound 2b: light yellow oil. IR (KBr): 3450, 3057, 2958, 2929, 2871, 1655, 1604, 1569, 1487, 1465, 1444, 1408, 1380, 1312, 1179, 746, 648, 600 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 7.44-7.46 (d, 2 H, J = 8.0 Hz), 7.22-7.28 (d, 2 H, J = 8.0 Hz), 6.93-7.07 (m, 5 H), 4.97 (s, 1 H), 4.22 (s, 1 H), 2.32 (s, 3 H), 2.23-2.28 (t, 2 H), 1.81-1.83 (m, 1 H), 1.39-1.60 (m, 2H), 1.21-1.28 (m, 2 H), 0.97-1.08 (d, 6 H), 0.72-0.80 (t, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 200.48, 146.31, 143.19, 140.63, 137.78, 134.85, 130.23, 129.67, 128.63, 128.43, 127.96, 79.88, 33.91, 32.38, 31.85, 21.51, 19.58, 19.09, 13.38. MS: m/z (%) = 382 (0.70) [M⁺], 381 (2.22) [M⁺ - 1], 367 (8.44), 366 (26.86), 365 (100.00) [M⁺ - 17], 339 (20.65), 325 (1.68), 311 (5.45), 293 (4.55), 247 (15.08), 129 (12.58), 119 (86.85), 91 (48.55), 77 (5.78). Anal. Calcd for C₂₄H₃₀O₂S: C, 75.35; H, 7.90. Found C, 75.48; H, 7.85%. Compound 3b: light yellow oil. IR (KBr): 3416, 3056, 2957, 2926, 2870, 1658, 1604, 1572, 1487, 1465, 1443, 1408, 1382, 1312, 1294, 1263, 1187, 1074, 1030, 836, 746, 591 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 8.04-8.06 (d, 2 H, J = 8.0 Hz), 7.28-7.50 (m, 7 H, J = 8.0 Hz), 4.96 (s, 1 H), 3.98 (s, 1 H), 2.45 (s, 3 H), 2.08-2.12 (t, 2 H), 1.55-1.64 (m, 1 H), 1.28-1.44 (m, 2 H), 1.17-1.19 (m, 2 H), 0.83-1.01 (d, 6 H), 0.64-0.67 (t, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 198.03, 143.95, 141.56, 140.16, 136.48, 135.46, 130.26, 129.72, 129.32, 129.11, 128.33, 79.36, 33.25, 31.91, 31.62, 21.97, 19.75, 19.01, 13.32. MS: m/z (%) = 381 (1.66) [M⁺ - 1], 367 (0.95), 366 (2.31), 365 (8.53) [M⁺ - 17], 339 (11.49), 295 (2.92), 293 (2.24), 205 (16.32), 119 (100.00), 77 (9.35). Anal. Calcd for C₂₄H₃₀O₂S: C, 75.35; H, 7.90. Found C, 75.52; H, 7.73%.