The head-to-head reductive coupling of homoallylic alcohols promoted by titanium(II)-olefin complexes

被引：0
|
作者：
Isakov, VE [1 ]
Kulinkovich, OG [1 ]
机构：
[1] Belarusian State Univ, Dept Organ Chem, Minsk 220050, BELARUS
来源：
SYNLETT | 2003年 / 07期
关键词：
titanium alkoxides; Grignard reagents; homoallylic alcohols; reductive coupling;
D O I：
暂无
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
Reaction of homoallylic alcohols 1a-e with i-PrMgBr in the presence of Ti(i-PrO)(4) leads to the unbranched saturated diols 2a-e as the main products in moderate to good yields. The head-to-head regioselectivity in reductive coupling of 4-penten-1-ol and 5-hexen-2-ol was also observed. Coupling of 2-methyl-5-hexen-2-ol, as well as unsaturated alcohols in which vinyl and hydroxyl groups are more distant from one another, proceeded with head-to-tail or tail-to-tail regioselectivity. It is supposed, that the unusual head-to-head regioselectivity in reductive coupling of homoallylic alcohols la-e is due to the formation of the key titanacyclopentane intermediates F and G having two fused oxatitanacyclopentane rings.
引用
收藏
页码：967 / 970
页数：4
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