Mechanism of Electrochemical Generation and Decomposition of Phthalimide-N‑oxyl

Mechanism of Electrochemical Generation and Decomposition of Phthalimide-N‑oxyl

Phthalimide N-oxyl (PINO) is a potent hydrogen atom transfer (HAT) catalyst that can be generated electrochemically from N-hydroxyphthalimide (NHPI). However, catalyst decomposition has limited its application. This paper details mechanistic studies of the generation and decomposition of PINO under...

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Veröffentlicht in:Journal of the American Chemical Society 2021-07, Vol.143 (27), p.10324-10332
Hauptverfasser: Yang, Cheng, Farmer, Luke A, Pratt, Derek A, Maldonado, Stephen, Stephenson, Corey R. J
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container_end_page 10332
container_issue 27
container_start_page 10324
container_title Journal of the American Chemical Society
container_volume 143
creator Yang, Cheng
Farmer, Luke A
Pratt, Derek A
Maldonado, Stephen
Stephenson, Corey R. J
description Phthalimide N-oxyl (PINO) is a potent hydrogen atom transfer (HAT) catalyst that can be generated electrochemically from N-hydroxyphthalimide (NHPI). However, catalyst decomposition has limited its application. This paper details mechanistic studies of the generation and decomposition of PINO under electrochemical conditions. Voltammetric data, observations from bulk electrolysis, and computational studies suggest two primary aspects. First, base-promoted formation of PINO from NHPI occurs via multiple-site concerted proton–electron transfer (MS-CPET). Second, PINO decomposition occurs by at least two second-order paths, one of which is greatly enhanced by base. Optimal catalytic efficiency in PINO-catalyzed oxidations occurs in the presence of bases whose corresponding conjugate acids have pK a’s in the range of ∼11–15, which strikes a balance between promoting PINO formation and minimizing its decay.
doi_str_mv 10.1021/jacs.1c04181
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