Preparation of α-silyl- or α,α-bis(silyl)-substituted alkylcopper reagents and their synthetic use
摘要:
Treatment of chlorobis(methyldiphenylsilyl)methyllithium with various alkyl and aryl Grignard reagents and CuCN center dot 2LiCl afforded 1,1-disilylalkylcopper species. The aerobic oxidation of the resulting copper reagents provided a variety of acylsilanes in good yields. Meanwhile, treatment of dichloro(methyldiphenylsilyl)methyllithum with Bu2CuLi center dot LiCN provided 1-cyano-1-silylalkylcopper species via consecutive double 1,2-migration of alkyl and cyano groups. (c) 2005 Elsevier Ltd. All rights reserved.
Treatment of chlorobis(methyldiphenylsilyl)methyllithium with vinylic Grignard reagents and CuCN·2LiCl afforded α,α-bis(silyl)-substituted allylic copper species. The reactions of the reagents with electrophiles provided a variety of 1,1-disilylalkenes.
Diorganophosphide anions, which usually function as nontransferable ligands on mixed cuprates, undergo smooth 1,2-migration on ate-type copper carbenoids. Phosphinodisilylmethylcoppers prepared by this protocol are converted into the corresponding phosphines, which can be used as bulky, highly basic and air-stable ligands.
Preparation of α-silyl- or α,α-bis(silyl)-substituted alkylcopper reagents and their synthetic use
Treatment of chlorobis(methyldiphenylsilyl)methyllithium with various alkyl and aryl Grignard reagents and CuCN center dot 2LiCl afforded 1,1-disilylalkylcopper species. The aerobic oxidation of the resulting copper reagents provided a variety of acylsilanes in good yields. Meanwhile, treatment of dichloro(methyldiphenylsilyl)methyllithum with Bu2CuLi center dot LiCN provided 1-cyano-1-silylalkylcopper species via consecutive double 1,2-migration of alkyl and cyano groups. (c) 2005 Elsevier Ltd. All rights reserved.
Facile Synthesis of Acylsilanes via Aerobic Oxidation of <i>g</i><i>em-</i>Disilylalkylcopper Compounds