SYNTHESIS AND REACTIONS OF (E)-1,4-BIS(SILYL)-SUBSTITUTED ENYNES

CE)-M-Bis(silyl)- and (£)-l,4-bis(disilanyl)but-l-en-3-ynes have been synthesized by the reaction of ethynyl-substituted mono- and disilanes with a catalytic amount of chlorotris(triphenylphosphine)rhodium(I) at room temperature in high yields. Similar reaction of 1-hexyne gave 2-butyloct-l-en-3-yne, while phenylacetylene afforded a mixture of 2,4-diphenylbut-l-en-3-yne and l,4-diphenylbut-l-en-3-yne in low yields. The reaction of (E)-l,4-bis(methyldiphenylsilyl)but-l-en-3-yne (2a) with 1 equiv of methyllithium followed by methyl iodide gave (E)-l-(methyldiphenylsilyl)pent-l-en-3-yne. Similar treatment of l,4-bis(l-phenyltetramethyldisilanyl)but-l-en-3-yne with methyllithium followed by hydrolysis produced l-(l-phenyltetramethyldisilanyl)but-l-en-3-yne. The reaction of 2a with methanol in the presence of a catalytic amount of sodium methoxide afforded l-(methyldiphenylsilyl)but-l-en-3-yne, which reacted with hydrosilanes in the presence of a platinum catalyst to give (E,E)-1.4-bis(silyl)buta-1.3-dienes. © 1990, American Chemical Society. All rights reserved.