Photoelectrochemical heterodifunctionalization of olefins : carboamidation using unactivated hydrocarbons

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Schmid, Simon and Wu, Shangze and Dey, Indrasish and Domański, Michał and Tian, Xianhai and Barham, Joshua P. (2024) Photoelectrochemical heterodifunctionalization of olefins : carboamidation using unactivated hydrocarbons. ACS Catalysis, 14 (13). pp. 9648-9654. ISSN 2155-5435 (https://doi.org/10.1021/acscatal.4c02320)

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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.

ORCID iDs

Schmid, Simon, Wu, Shangze, Dey, Indrasish, Domański, Michał, Tian, Xianhai and Barham, Joshua P. ORCID logoORCID: https://orcid.org/0000-0003-1675-9399;
CORE (COnnecting REpositories)