ASYMMETRIC-SYNTHESIS OF ALPHA-AMINO-ACIDS BY COPPER-CATALYZED CONJUGATE ADDITION OF GRIGNARD-REAGENTS TO OPTICALLY-ACTIVE CARBAMATOACRYLATES

被引：62

作者：

LANDER, PA ^{[1
]}

HEGEDUS, LS ^{[1
]}

机构：

[1] COLORADO STATE UNIV,DEPT CHEM,FT COLLINS,CO 80523

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1994年 / 116卷 / 18期

关键词：

D O I：

10.1021/ja00097a020

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Optically active ene carbamates were alpha-lithiated by lithium tetramethylpiperidide in the presence of trialkylstannyl chlorides to produce alpha-stannylated compounds. These underwent facile palladium-catalyzed couplings with acid chlorides to produce alpha-keto ene carbamates in good yield. Treatment of the alpha-stannyl ene carbamates with butyllithium followed by quenching with carbon dioxide and esterification gave optically active carbamatoacrylates. Copper-catalyzed addition of tert-butyl-, 1-naphthyl-, 2-propenyl-, p-methoxyphenyl-, (trimethylsilyl)methyl-, cyclohexyl-, 1-adamantyl-, and isopropyl Grigard reagents followed by quenching at -10 to 25 degrees C and removal of the protecting groups gave the corresponding alpha-amino acids in 70-90% yield and 73-97% ee. Quenching the reaction at low temperature resulted in little if any asymmetric induction.

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页码：8126 / 8132

页数：7

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