REVERSIBLE GRIGNARD AND ORGANOLITHIUM REACTIONS
REVERSIBLE GRIGNARD AND ORGANOLITHIUM REACTIONS
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DOI：
10.1021/ja00475a026
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发表时间：
1978-01-01
影响因子：
15
通讯作者：
MOZDZEN, EC
中科院分区：
文献类型：
--
作者：
BENKESER, RA;SIKLOSI, MP;MOZDZEN, EC
本文给出了烯丙基型格氏试剂和有机锂试剂与各种酮底物的可逆加成反应的许多实例。空间位阻在这些可逆加成中的作用被清楚地证明。已设计出从巴豆基有机金属衍生的异构纯的甲基烯丙基甲醇的纯化方法。当-甲基烯丙基甲醇的醇盐发生逆转时，偶尔形成的酮是由酮烯醇化物形成的结果。最后，它已被证明，并不是所有的巴豆基甲醇时产生的巴豆基有机金属化合物与受阻酮反应必然导致从最初形成的甲基烯丙基异构体的异构化。
Numerous examples are given of the reversible addition of allylic-type Grignard and organolithium reagents to a va-riety of ketone substrates. The role of steric hindrance in these reversible additions is clearly demonstrated. Procedures have been devised for the preparationof isomerically pure-methallylcarbinols derived from the crotyl organometallic. The ketones which form occasionally when the alkoxides of the-methallylcarbinols undergo reversal result from the formation of the ke-tone enolates. Finally, it has been shown that not all of the crotylcarbinols produced when crotyl organometallics react with hindered ketones necessarily result from an isomerization of the initially formed-methallyl isomers.