Co(thd)2:: a superior catalyst for aerobic epoxidation and hydroperoxysilylation of unactivated alkenes:: application to the synthesis of spiro-1,2,4-trioxanes

被引：68

作者：

O'Neill, PM ^{[1
]}

Hindley, S

Pugh, MD

Davies, J

Bray, PG

Park, BK

Kapu, DS

Ward, SA

Stocks, PA

机构：

[1] Univ Liverpool, Robert Robinson Labs, Dept Chem, Liverpool L69 7ZD, Merseyside, England

[2] Univ Liverpool, Dept Pharmacol, Liverpool L69 3GE, Merseyside, England

[3] Univ Liverpool, Liverpool Sch Trop Med, Liverpool L3 5QA, Merseyside, England

来源：

TETRAHEDRON LETTERS | 2003年 / 44卷 / 44期

基金：

英国生物技术与生命科学研究理事会; 英国工程与自然科学研究理事会;

关键词：

D O I：

10.1016/j.tetlet.2003.09.033

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Bis(2,2;6,6-tetramethyl-3,5-heptanedionato)cobalt(II) (Co(thd)(2)), a beta-diketonate prepared in a simple one-step procedure, is an excellent catalyst for aerobic epoxidation and Mukaiyama-Isayama hydroperoxysilylation of unactivated alkenes. For hydroperoxysilylation, Co(thd)(2) is superior to Co(acac)(2) and can catalyse oxidation of cyclic alkenes in excellent yield. Chiral beta-diketonate or keto iminato catalysts failed to catalyse this reaction in an enantioselective manner and a free radical mechanism consistent with this observation is proposed. Hydroperoxysilylation of cyclohex-1-enylmethanol by Co(thd)(2) followed by addition of a ketone/TsOH provides a simple one-pot procedure for the synthesis of spiro-1,2,4-trioxane antimalarials. (C) 2003 Published by Elsevier Ltd.

引用

页码：8135 / 8138

页数：4

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