手性二硼模板双亚胺的不对称分子内还原偶联

IF 7.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science Pub Date : 2025-06-17 DOI:10.1039/d5sc03633j

Tian Chen, Hao-Yang Wang, Ronghua Xu, Guangqing Xu, He Yang, Jiangtao Sun, Lung Wa Chung, Wenjun Tang

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引用次数: 0

摘要

首次在温和条件下，以双（(+)-蒎烯二醇酯）二硼为模板，完成了双亚胺的分子内不对称还原偶联反应，得到了前所未有的手性高收率、优异对映选择性的二氢菲-9,10-顺式二胺。手性外环顺二胺产物是不对称催化的有效手性配体。DFT研究强调了少见的扭曲船形通路（而不是常见的椅子型）和空间效应在排他形成顺二胺和实现高对映选择性中的关键作用。这种还原耦合方案代表了二硼促进的[3,3]-符号重排的显著扩展。

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Asymmetric Intramolecular Reductive Coupling of Bisimines Templated by Chiral Diborons

An asymmetric intramolecular reductive coupling of bisimines has been accomplished for the first time under mild conditions with bis((+)-pinanediolato)diboron as the template, providing the unprecedented chiral dihydrophenanthrene-9,10-cis-diamines in high yields and excellent enantioselectivities. The chiral exocyclic cis-diamine products have served as effective chiral ligands for asymmetric catalysis. DFT study highlights the crucial roles of uncommon twisted-boat pathway (instead of the common chair type) and the steric effect in exclusively forming the cis-diamines and achieving high enantioselectivity. This reductive coupling protocol represents a significant expansion of the diboron-promoted [3,3]-sigmatropic rearrangement.

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来源期刊

Chemical Science CHEMISTRY, MULTIDISCIPLINARY-

CiteScore

14.40

自引率

4.80%

发文量

1352

审稿时长

2.1 months

期刊介绍： Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.