Titanacyclopropanes as versatile intermediates for carbon-carbon bond formation in reactions with unsaturated compounds

被引：36

作者：

Kulinkovich, OG ^{[1
]}

机构：

[1] Belarusian State Univ, Dept Chem, Minsk 220080, BELARUS

来源：

PURE AND APPLIED CHEMISTRY | 2000年 / 72卷 / 09期

关键词：

D O I：

10.1351/pac200072091715

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Dialkoxytitanacyclopropane intermediates [or titanium (II)-olefin complexes] generated in situ from ethylmagnesium bromide and titanium (IV) isopropoxide react with allylic alcohols and allylic ethers to afford S(N)2' allylic ethylation products. The reaction proceeds with high regioselectivity and with low to high trans-/cis- stereoselectivity. This observation and others suggest a reaction mechanism involving an EtMgBr-initiated formation of titanacyclopentane ate complex 10 from titanacyclopropane-olefin complex 7 as a key step. Based on this assumption, a modified mechanism of titanium-mediated cyclopropanation of esters with Grignard reagents is proposed.

引用

页码：1715 / 1719

页数：5

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