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手性N-膦酰基亚胺化学：用于β-氨基酸合成的酯烯醇盐的不对称加成反应

Chiral N-phosphonyl imine chemistry: asymmetric additions of ester enolates for the synthesis of beta-amino acids.

作者信息

Han Jianlin, Ai Teng, Nguyen Thao, Li Guigen

机构信息

Department of Chemistry & Biochemistry, Texas Tech University, Lubbock, TX 79401-1061, USA.

出版信息

Chem Biol Drug Des. 2008 Aug;72(2):120-6. doi: 10.1111/j.1747-0285.2008.00682.x. Epub 2008 Jul 9.

DOI:10.1111/j.1747-0285.2008.00682.x
PMID:18631372
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC2575089/
Abstract

Chiral phosphonyl imines attached by 1-naphthyl protection group were found to react with lithium ester enolates smoothly and give chiral beta-amino esters in good yields (70-88%) and up to excellent diastereoselectivity (>99:1 dr). Triisopropoxytitanium (IV) chloride was found to enhance diastereoseletivity when used as the Lewis acid promoter. The chiral auxiliary can be readily removed by treating with HBr to give free amino esters. The absolute structure has been unambiguously determined by converting one of the products into an authentic sample. This reaction provides an easy access to beta-amino acid derivatives.

摘要

发现带有1-萘基保护基的手性磷酰亚胺能与锂酯烯醇盐顺利反应，以良好的产率（70 - 88%）得到手性β-氨基酯，且具有高达优异的非对映选择性（>99:1 dr）。发现三异丙氧基钛（IV）氯化物用作路易斯酸促进剂时可提高非对映选择性。通过用HBr处理可轻松除去手性助剂，得到游离的氨基酯。通过将其中一种产物转化为真实样品，已明确确定了绝对结构。该反应为β-氨基酸衍生物提供了一种简便的合成方法。

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本文引用的文献

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Asymmetric C-C Bond Formation between Chiral -Phosphonyl Imines and Ni(II)-Complex of Glycine Schiff Base Provides a GAP Synthesis of α,β--Diamino Acid Derivatives.手性膦酰亚胺与甘氨酸席夫碱镍（II）配合物之间的不对称C-C键形成实现了α，β-二氨基酸衍生物的间隙合成。
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