H. Westmijze, Henk Kleijn, P. Vermeer
1984
Citations
0
Influential Citations
17
Citations
Journal
Journal of Organometallic Chemistry
Abstract
Abstract Ethynylsilanes (I) are converted into α-silyl substituted (Z)-alkenylcopper(I) compounds (II) by treatment with RCu reagents. The adducts II react with a variety of electrophiles to give the 1-alkenylsilanes RCHC(E)SiR 3 ′ (III: E = H, Cl, Br, I, CN, SnMe 3 , SMe, Me, H 2 CHCH 2 ). The conversion of I into III (E = H) can also be effected by using homocuprates, R 2 CuMgCl, and triorganodicuprates, R 3 Cu 2 MgCl. The latter reagent should be used when the group R is methyl. An interesting 1,3-diene formation is observed on treating excess of ethynyltrimethylsilane (Ib) with R 3 Cu 2 MgCl; this reaction involves addition of intermediary vinylcuprates to unreacted 1-alkynylsilane (Ib). The intermediary 1,3-dienyl adduct (VIIb) reacts with various electrophiles to give 1,3-dienes, RCHC(SiMe 3 )CHC(E)SiMe 3 (VIIIb).