A Convenient Preparation of Chalcogenoenynes from β-Bromovinyl Ketene Chalcogenoacetals

Abstract

β-Bromovinyl ketene chalcogenoacetals have been synthesized stereoselectively via electrophilic addition of the benzeneselenenyl bromide to substituted alkynes. The palladium-catalyzed cross-coupling reaction of β-bromovinyl ketene chalcogenoacetals with 1-alkynes gave the corresponding chalcogenoenynes in 62-85% yields

Key-words

cross-coupling - chalcogenoenynes - palladium - tellurium - selenium - β-bromovinyl ketene chalcogenoacetals

References

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19

Pd(0) Catalyzed Cross-Coupling Reaction of β-Bromovinyl Ketene Chalcogenoacetals 2b with 1-Hexyne; General Procedure: To a solution of Pd(PPh₃)
(5 mol%, 0.058 g), in pyrrolidine (5 mL) at r.t. under Ar atmosphere, were added of β-bromovinyl ketene chalcogenoacetals 2b (0.425 g, 1 mmol) and hexyne (0.164 g, 2 mmol). The mixture was stirred at r.t. for 10 h, treated with NH₄Cl saturated solution (5 mL) and then extracted with EtOAc. The organic layer was washed with brine and dried over MgSO₄. The solvent was evaporated and the residue was purified by flash silica gel chromatography eluted with hexane to yield 3a in 65% yield (0.276 g). ¹H NMR (200 MHz, CDCl₃): δ = 7.74-7.41 (m, 2 H), 7.39-7.25 (m, 3 H), 2.46 (s, 3 H), 2.40 (t, J = 7.0 Hz, 2 H,), 1.63-1.25 (m, 8 H), 1.35-1.06 (m, 4 H), 0.95 (t, J = 7.0 Hz, 3 H), 0.92 (t, J = 7.0 Hz, 3 H). ¹³C NMR (50 MHz, CDCl₃): δ = 140.56, 135.02, 129.32, 128.85, 127.77, 116.11, 98.89, 76.90, 33.87, 31.13, 30.69, 28.11, 22.14, 21.95, 19.28, 16.70, 13.81, 13.50. IR (neat, cm^-1): 2929, 2859, 2360, 1699, 1377. LRMS (rel. int.): m/z = 426 (10), 332 (48) 270 (100), 176 (30), 71 (42), 57 (38).