TERTIARY CARBINAMINES BY ADDITION OF ORGANOCERIUM REAGENTS TO NITRILES AND KETIMINES

被引:78
作者
CIGANEK, E
机构
[1] The Du Pont Merck Pharmaceutical Co., Inc., Wilmington
关键词
D O I
10.1021/jo00042a037
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Organocerium reagents, prepared by reaction of aromatic and primary and secondary alkyllithium reagents with anhydrous cerium chloride, add to nitriles twice to give tertiary carbinamines in often excellent yields. Addition of n-BuCeCl2 to acetophenone is about 4 times faster than addition to benzonitrile. Only 1,2-diaddition is observed in the reaction of MeCeCl2 with cinnamonitrile. The species formed in the double addition of organocerium reagents to nitriles are sufficiently basic to generate a benzyne intermediate by abstraction of an aromatic proton and nucleophilic enough to undergo an intramolecular Chichibabin reaction. Reaction of N-unsubstituted ketimines or their lithium salts with organocerium reagents permits the synthesis of tertiary carbinamines with three different groups on the tertiary carbon center.
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页码:4521 / 4527
页数:7
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