手性双膦催化的不对称施陶丁格/阿扎-维蒂希反应：开发、机理研究和合成应用

IF 1.7 4区化学 Q3 CHEMISTRY, ORGANIC

Synlett Pub Date : 2024-08-22 DOI:10.1055/s-0043-1775038

Hongzhi Yang, Truc Quynh Nguyen, Yefeng Tang

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引用次数: 0

摘要

通过前所未有的手性双膦催化不对称施陶丁格/扎-维蒂希反应，实现了 2,2-二取代环己烷-1,3-二酮的对映选择性去对称化。这项工作取得成功的关键在于利用了一种电子丰富、立体受阻的手性双膦试剂（即 DuanPhos）作为催化剂。此外，还建立了一个独特的还原体系，以解决必要的 PIII/PV = O 氧化还原循环。通过计算和实验相结合的研究，阐明了手性双膦催化不对称 Staudinger/aza-Wittig 反应的机理。利用新开发的方法，简明地合成了几种克林类金丝桃科生物碱。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Chiral-Bisphosphine-Catalyzed Asymmetric Staudinger/Aza-Wittig Reaction: Development, Mechanism Study, and Synthetic Application

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Chiral-Bisphosphine-Catalyzed Asymmetric Staudinger/Aza-Wittig Reaction: Development, Mechanism Study, and Synthetic Application

The enantioselective desymmetrization of 2,2-disubstituted cyclohexane-1,3-diones has been realized through an unprecedented chiral-bisphosphine-catalyzed asymmetric Staudinger/aza-Wittig reaction. The key to this work’s success lies in utilizing an electronically rich and sterically hindered chiral bisphosphine reagent, namely DuanPhos, as a catalyst. In addition, a unique reductive system was established to address the requisite P^III/PV = O redox cycle. The mechanism of the chiral-bisphosphine-catalyzed asymmetric Staudinger/aza-Wittig reaction has been elucidated through combined computational and experimental studies. Several crinine-type amaryllidaceae alkaloids have been synthesized concisely, hinging on the newly developed methodology.

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来源期刊

Synlett 化学-有机化学

CiteScore

3.40

自引率

5.00%

发文量

369

审稿时长

1 months

期刊介绍： SYNLETT is an international journal reporting research results and current trends in chemical synthesis in short personalized reviews and preliminary communications. It covers all fields of scientific endeavor that involve organic synthesis, including catalysis, organometallic, medicinal, biological, and photochemistry, but also related disciplines and offers the possibility to publish scientific primary data.