光催化氧化活化双环[1.1.0]丁烷的正式[2σ+2π]环加成反应

IF 13.1 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2024-09-06 DOI:10.1021/acscatal.4c0506710.1021/acscatal.4c05067

Maxim Golfmann, Marius Reinhold, Jorn D. Steen, Malte S. Deike, Behrend Rodemann, Christopher Golz, Stefano Crespi* and Johannes C. L. Walker*,

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引用次数: 0

摘要

我们报告了氧化双环[1.1.0]丁烷活化的一个发现实例。这种反应性与成熟的应变释放亲核加成和还原活化形成鲜明对比，为在合成中利用双环[1.1.0]丁烷开辟了更多可能性。利用强氧化性吖啶鎓有机光催化剂，双环[1.1.0]丁烷与烯烃或醛类进行形式上的[2σ+2π]环加成，可生成相应的双环[2.1.1]己烷或氧杂双环[2.1.1]己烷。双环[1.1.0]丁烷和烯的特性之间的微妙相互作用决定了反应的机理，区域差异途径提供了互补的反应产物，其区域选择性高达 20:1。包括电化学、光物理、自由基捕获和计算研究在内的机理研究支持所提出的氧化机理。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Photocatalytic Oxidative Activation of Bicyclo[1.1.0]butanes for Formal [2σ+2π] Cycloadditions

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Photocatalytic Oxidative Activation of Bicyclo[1.1.0]butanes for Formal [2σ+2π] Cycloadditions

We report the discovery of an example of oxidative bicyclo[1.1.0]butane activation. This reactivity stands in contrast to well-established strain-release nucleophile addition and reductive activation and opens up further possibilities for exploiting bicyclo[1.1.0]butanes in synthesis. Using a strongly oxidizing acridinium organophotocatalyst, the formal [2σ+2π] cycloaddition between bicyclo[1.1.0]butanes and alkenes or aldehydes leads to the corresponding bicyclo[2.1.1]hexanes or oxabicyclo[2.1.1]hexanes. The subtle interplay between bicyclo[1.1.0]butane and alkene identity dictates the mechanism of the reaction, with regiodivergent pathways providing complementary reaction products in up to >20:1 regioselectivity. A mechanistic investigation including electrochemical, photophysical, radical trapping, and computational studies support the oxidative mechanisms proposed.

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.