Photoredox-Catalyzed Difluoromethylation of Dehydroalanine and Dehydroalanine-Containing Dipeptides: A Proof-of-Concept Enantioselective Variant

IF 4.7 1区化学 Q1 CHEMISTRY, ORGANIC

Organic Letters Pub Date : 2026-10-16 Epub Date: 2026-10-02 DOI:10.1021/acs.orglett.6c03908

Yue Zhang, Hangzhi Jiang, Shengqun Zhang, Yiqian Li, Tianshuai Zhu, Guangwei Wu, Jing-Jing Zhang, Xingfeng Bai, Zhen Chen

引用次数: 0

Abstract

A photoredox-catalyzed difluoromethylation of dehydroalanine (Dha) derivatives and protected Dha-containing dipeptides is described. The reaction enables direct installation of the CF₂H group to access β-difluoromethyl α-amino acid derivatives under mild conditions using difluoromethyl sulfone as the radical precursor. A proof-of-concept CPA-enabled enantioselective variant furnished the model product in 55% isolated yield and 73% ee. Mechanistic experiments support a radical–polar crossover pathway and suggest that reversible product deprotonation may contribute to stereochemical erosion.

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光氧化还原催化脱氢丙氨酸和含脱氢丙氨酸二肽的二氟甲基化：概念验证的对映体选择性变体

摘要描述了光氧化还原催化脱氢丙氨酸（Dha）衍生物和含Dha保护二肽的二氟甲基化反应。该反应使CF2H基团在温和的条件下以二氟甲基砜为自由基前体直接安装获得β-二氟甲基α-氨基酸衍生物。一个概念验证的cpa对映选择变体提供了55%的分离收率和73%的ee模型产品。机械实验支持自由基-极性交叉途径，并表明可逆产物去质子化可能有助于立体化学侵蚀。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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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.