Functionalisation of tetraalkylsilanes derived from C-H activation; towards annulations of diterpenoids

被引：13

作者：

Harris, PWR ^{[1
]}

Rickard, CEF ^{[1
]}

Woodgate, PD ^{[1
]}

机构：

[1] Univ Auckland, Dept Chem, Auckland, New Zealand

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2000年 / 601卷 / 01期

关键词：

ruthenium catalysis; aromatic ketones; tetraalkylsilane; bromination/desilylation; oxidation;

D O I：

10.1016/S0022-328X(00)00059-0

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Vinyl trialkylsilanes are efficient substrates for use in the ortho alkylation of aromatic ketones catalysed by zerovalent ruthenium complexes, giving, e.g. (2-trimethylsilylethyl)acetophenones. Methods for the selective desilylation-functionalisation of such tetraalkylsilanes are investigated. Some diterpenoid tetraalkylsilanes derived from the ruthenium-catalysed insertion of vinyltrimethylsilane have been functionalised by benzylic bromination of an ArCH2CH2SiMe3 fragment with NaBrO3-Na2S2O5 (optimally), leading to a 1,2-dibromoethyl derivative. Further transformations culminated in the overall conversion of ArCH2CH2SiMe3 into ArCOCH3. Attempted aldol coupling of the resulting 1,4-diketone provoked skeletal reorganisation. A tetraalkylsilane was converted into a silanol (ArCH2CH2SiMe2OH) by the action of aluminium chloride and water, but further oxidation of this silanol to the primary alcohol (ArCH2CH2OH) was unsuccessful. (C) 2000 Elsevier Science S.A. All rights reserved.

引用

页码：172 / 190

页数：19

共 45 条

[1] CLEAVAGE OF SI-C BONDS BY TRANSITION-METAL COMPOUNDS - METHYLATION AND PHENYLATION OF OLEFINS BY ORGANOSILICON COMPOUNDS IN PRESENCE OF PALLADIUM SALTS [J].