Photoelectrochemical Heterodifunctionalization of Olefins: Carboamidation Using Unactivated Hydrocarbons

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL ACS Catalysis Pub Date : 2024-06-12 DOI:10.1021/acscatal.4c02320

Simon Schmid, Shangze Wu, Indrasish Dey, Michał Domański, Xianhai Tian* and Joshua P. Barham*,

引用次数: 0

Abstract

A mild carboamidation of electronically different styrenes with diverse hydrocarbons was developed by merging photocatalysis and electrochemistry without using external oxidants. The reaction proceeds through a tandem photocatalytic hydrogen atom transfer (HAT), radical addition to styrenes, radical polar crossover, and subsequent Ritter-type amidation. Key to engaging unactivated alkanes is the use of tetrabutylammonium decatungstate (TBADT) as a HAT photocatalyst, which is regenerated from its reduced form by anodic oxidation. A diverse set of C–H precursors, including alkanes, was successfully utilized. Styrenes bearing different functionalities in their arene rings were selectively difunctionalized. Overall, we demonstrate how photoelectrochemistry forges unconventional reactivity by merging HAT with an oxidative radical polar crossover.

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烯烃的光电化学异二官能化：使用未活化碳氢化合物进行羰基化反应

在不使用外部氧化剂的情况下，通过将光催化与电化学相结合，开发出了一种温和的电子不同苯乙烯与不同烃类的羧酰胺化反应。该反应通过串联光催化氢原子转移（HAT）、苯乙烯的自由基加成、自由基极性交叉以及随后的里特式酰胺化反应进行。使用癸钨酸四丁基铵（TBADT）作为 HAT 光催化剂是处理未活化烷烃的关键，TBADT 可通过阳极氧化从其还原形式再生。包括烷烃在内的各种 C-H 前体都得到了成功利用。在炔环中具有不同官能度的苯乙烯被选择性地进行了双官能度化。总之，我们展示了光电化学是如何通过将 HAT 与氧化自由基极性交叉融合来实现非常规反应的。

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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.