Catalytic Asymmetric Synthesis of Cyclopentyl β-Amino Esters by [3+2] Cycloaddition of Enecarbamates with Electrophilic Metalloenolcarbene Intermediates

被引：28

作者：

Deng, Yongming ^{[1
]}

Yglesias, Matthew V. ^{[1
]}

Arman, Hadi ^{[1
]}

Doyle, Michael P. ^{[1
]}

机构：

[1] Univ Texas San Antonio, Dept Chem, One UTSA Circle, San Antonio, TX 78249 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2016年 / 55卷 / 34期

基金：

美国国家科学基金会;

关键词：

amino acids; cycloaddition; diazo compounds; enantioselectivity; rhodium; ENANTIOSELECTIVE INTERMOLECULAR CYCLOADDITION; CHIRAL DIRHODIUM(II) CARBOXYLATES; IRELAND-CLAISEN REARRANGEMENTS; ACID-DERIVATIVES; C(5)-SUBSTITUTED TRANSPENTACINS; MEDICINAL CHEMISTRY; ORGANIC-SYNTHESIS; CARBONYL YLIDES; HYDROGENATION; ENAMIDES;

D O I：

10.1002/anie.201605438

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Chiral cyclopentyl beta-amino esters are formed catalytically by [3+2] cycloaddition reactions of enecarbamates with electrophilic metalloenolcarbenes in high yield with up to 98% ee and excellent diastereocontrol. Use of beta-silyl-substituted enoldiazoacetates with a chiral dirhodium catalyst and trans-beta-arylvinylcarbamates are optimal for this transformation, which occurs with hydrogen-bond association between the vinylcarbamate and the intermediate metalloenol-carbene. Reductive conversion of the protected amino esters forms highly functionalized cyclopentyl beta-amino acids and 3-aminocyclopentanones.

引用

页码：10108 / 10112

页数：5

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