Large scale enantiomeric synthesis, purification, and characterization of ω-unsaturated amino acids via a Gly-Ni(II)-BPB-complex

被引：32

作者：

Gu, XY ^{[1
]}

Ndungu, JA ^{[1
]}

Qiu, W ^{[1
]}

Ying, JF ^{[1
]}

Carducci, MD ^{[1
]}

Wooden, H ^{[1
]}

Hruby, VJ ^{[1
]}

机构：

[1] Univ Arizona, Dept Chem, Tucson, AZ 85721 USA

来源：

TETRAHEDRON | 2004年 / 60卷 / 37期

基金：

美国国家科学基金会;

关键词：

Ni(Il)-complex chiral auxiliary; alkylation; diastereo-selectivity; epimerization; amino acids;

D O I：

10.1016/j.tet.2004.06.087

中图分类号：

O62 [有机化学];

学科分类号：

070303 [有机化学]; 081704 [应用化学];

摘要：

The enantiomeric syntheses of omega-unsaturated amino acids and beta-substituted omega-unsaturated amino acids were accomplished by using Gly-Ni-2[N-(N'-benzylprolyl)amino]benzophenone (BPB) as a chiral auxiliary. The synthesis provides excellent yields and high diastereoselectivities. The product crystallization followed by isomer epimerization strategy makes the reaction practical and useful for large-scale preparations. Dialkylation of the Ni(II)-complex, which was designed for mechanistic considerations, revealed that high diastereoselectivity is obtained due to the thermodynamic conformational stability of the Ni(II)-complex. The assignment of absolute configuration was accomplished by NMR, which is supported by corresponding X-ray structure and optical rotation data. Both enantionnerically pure amino acids can be synthesized in this alkylation-hydrolysis two-step strategy in multi gram scales. (C) 2004 Elsevier Ltd. All rights reserved.

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页码：8233 / 8243

页数：11

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