A Stereoselective Synthesis of (E)-α-Stannylvinyl Sulfones via Palladium-­Catalyzed Hydrostannylation of Acetylenic Sulfones

Abstract

Palladium-catalyzed hydrostannylation of acetylenic sulfones with Bu₃SnH in benzene at room temperature afforded stereoselectively (E)-α-stannylvinyl sulfones in good to high yields.

hydrostannylation - acetylenic sulfone - palladium - (E)-α-stannylvinyl sulfone - stereoselective synthesis

References and Notes

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14

Typical Procedure for Hydrostannylation Reaction.
A 25-mL, two-necked round-bottomed flask equipped with a magnetic stir bar and argon was charged sequentially with 1-butyl-2-(phenylsulfonyl)ethyne (1a, 1 mmol), benzene (4 mL), Pd(PPh₃)₄ (0.01 mmol) and Bu₃SnH (1.05 mmol). The mixture was stirred at r.t. for 4 h. After removal of the solvent under reduced pressure, the residue was diluted with light PE (20 mL) and filtered to remove the palladium catalyst. The resulting solution was concentrated under vacuum and the residue was purified by flash chromatography on silica gel eluting with light PE.
Selected spectral and analytical data for 2a: yield 0.462 g (90%). ¹H NMR (400 MHz, CDCl₃): δ = 7.86-7.84 (m, 2 H), 7.56-7.48 (m, 3 H), 6.28 (t, J = 7.2 Hz, 1 H), 2.40-2.36 (m, 2 H), 1.56-1.48 (m, 6 H), 1.38-1.29 (m, 6 H), 1.22-1.15 (m, 4 H), 1.11-1.06 (m, 6 H), 0.90 (t, J = 7.2 Hz, 9 H), 0.80 (t, J = 7.2 Hz, 3 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 157.4, 149.0, 143.5, 132.5, 128.8, 127.1, 31.0, 30.6, 28.8, 27.3, 22.3, 13.8, 13.7, 11.4 ppm.

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19

Typical Procedure for Stille Coupling Reaction.
(E)-1-(Tributylstannyl)-1-(phenylsulfonyl)-1-hexene (2a, 1 mmol) and allyl bromide 3a (1.1 mmol) were dissolved in DMF (10 mL) under Ar at r.t. The compounds Pd(PPh₃)₄ (0.05 mmol) and CuI (0.75 mmol) were then added. The mixture was stirred at r.t. and monitored by TLC for the disappearance of the starting organostannane. Then it was diluted with Et₂O (40 mL) and the organic layer was washed with aq NH₄Cl (10 mL) and H₂O (20 mL), and dried over MgSO₄. The solvent was removed under reduced pressure and the residue purified by column chromatography on silica gel eluting with a mixture of Et₂O and light PE (1:6).
Selected spectral and analytical data for 4a: yield 0.219 g (83%). ¹H NMR (400 MHz, CDCl₃): δ = 7.90-7.87 (m, 2 H), 7.61-7.51 (m, 3 H), 6.03 (t, J = 7.6 Hz, 1 H), 5.73-5.63 (m, 1 H), 5.11-5.04 (m, 2 H), 3.08-3.06 (m, 2 H), 2.68-2.60 (m, 2 H), 1.37-1.25 (m, 4 H), 0.88 (t, J = 7.2 Hz, 3 H) ppm. ¹³C NMR (100 MHZ, CDCl₃): δ = 144.5, 141.5, 138.9, 134.3, 133.2, 129.1, 127.4, 118.0, 36.8, 31.3, 28.4, 22.3, 13.9 ppm.