Theoretical evidence for pyramidalized bicyclic serine enolates in highly diastereoselective alkylations

被引：33

作者：

Aydillo, Carlos ^{[1
]}

Jimenez-Oses, Gonzalo ^{[1
]}

Busto, Jesus H. ^{[1
]}

Peregrina, Jesus M. ^{[1
]}

Zurbano, Maria M. ^{[1
]}

Avenoza, Alberto ^{[1
]}

机构：

[1] Univ La Rioja, UA CSIC, Dept Quim, Logrono 26006, Spain

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2007年 / 13卷 / 17期

关键词：

ab initio calculations; alkylation; amino acids; asymmetric synthesis; carbanions;

D O I：

10.1002/chem.200601746

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A new chiral serine equivalent and its enantiomer have been synthesized from (S)- and (R)-N-Bocserine methyl esters (Boc: tert-butyloxycarbonyl). The use of these compounds as chiral building blocks has been demonstrated in the synthesis of alpha-alkyl alpha-amino acids by diastereoselective potassium enolate alkylation reactions and subsequent acid hydrolyses. Theoretical studies were performed to elucidate the stereochemical outcome of both the formation of five-membered cyclic N.O-acetals and the subsequent alkylation process, which occurs with total retention of configuration. This feature could be explained in terms of the high degree of pyramidalization of enolate intermediates.

引用

页码：4840 / 4848

页数：9

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