基于氰基自由基迁移的高非对映选择性合成5/6-熔融双环体系

IF 5 1区化学 Q1 CHEMISTRY, ORGANIC

Organic Letters Pub Date : 2025-03-03 DOI:10.1021/acs.orglett.5c0027010.1021/acs.orglett.5c00270

Chenxi Wu, Dan-Yang Wu, Yu-Hao Wang and Pu-Sheng Wang*,

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引用次数: 0

摘要

本文报道了一种高度非对映选择性的氰基转移自由基环化反应，在无催化剂和近紫外光照射条件下，以100%的原子经济性构建了具有三个连续和密集立体元素的5/6-熔合双环体系。机理研究和密度泛函理论计算表明，非对映选择性是由三元双自由基中间体的构象分布和自由基耦合前的逆向系统间交叉（RISC）速率决定的。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Highly Diastereoselective Synthesis of 5/6-Fused Bicyclic Ring Systems via Radical Cyano Group Migration

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Highly Diastereoselective Synthesis of 5/6-Fused Bicyclic Ring Systems via Radical Cyano Group Migration

Here we report a highly diastereoselective cyano group transfer radical cyclization reaction to construct 5/6-fused bicyclic ring systems that bear three contiguous and congested stereogenic elements, with 100% atom economy under catalyst-free and near-ultraviolet light irradiation conditions. Mechanistic investigations and density functional theory calculations suggest that the diastereoselectivity is governed by the conformational distribution of the triplet diradical intermediate and the rate of reverse intersystem crossing (RISC) before radical coupling.

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来源期刊

Organic Letters 化学-有机化学

CiteScore

9.30

自引率

11.50%

发文量

1607

审稿时长

1.5 months

期刊介绍： Organic Letters invites original reports of fundamental research in all branches of the theory and practice of organic, physical organic, organometallic,medicinal, and bioorganic chemistry. Organic Letters provides rapid disclosure of the key elements of significant studies that are of interest to a large portion of the organic community. In selecting manuscripts for publication, the Editors place emphasis on the originality, quality and wide interest of the work. Authors should provide enough background information to place the new disclosure in context and to justify the rapid publication format. Back-to-back Letters will be considered. Full details should be reserved for an Article, which should appear in due course.