不对称 NHC 催化的氮杂-Diels-Alder 反应：α-氨基酸衍生物的高对映选择性合成路线和 DFT 计算。

Asymmetric NHC-catalyzed aza-Diels-Alder reactions: highly enantioselective route to α-amino acid derivatives and DFT calculations.

机构信息

College of Materials, Chemistry and Chemical Engineering, Hangzhou Normal University , Hangzhou 310036, China.

出版信息

Org Lett. 2014 Aug 1;16(15):3872-5. doi: 10.1021/ol501424f. Epub 2014 Jul 2.

Abstract

A facile N-heterocyclic carbene catalytic enantioselective aza-Diels-Alder reaction of oxodiazenes with α-chloroaldehydes as dienophile precursors is reported, with excellent enantioselectivity (ee > 99%) and excellent yield (up to 93%). DFT study showed that cis-TSa, formed from a top face approach of oxodiazene to cis-IIa, is the most favorable transition state and is consistent with the experimental observations.

摘要

报道了一种简便的 N-杂环卡宾催化对映选择性氮杂 Diels-Alder 反应，以氧杂二氮烯作为亲二烯体前体与α-氯代醛反应，具有优异的对映选择性（ee>99%）和收率（高达 93%）。DFT 研究表明，cis-TSa 是最有利的过渡态，它是由氧杂二氮烯从 cis-IIa 的顶面接近形成的，与实验观察结果一致。