Additive-controlled chemoselective inter-/intramolecular hydroamination via electrochemical PCET process.

Beilstein J Org Chem

Graduate School of Engineering, Yokohama National University, 79-7 Tokiwadai, Hodogaya-ku, Yokohama, Kanagawa 240-8501, Japan.

Published: February 2024

AI Article Synopsis

  • Electrochemically generated amidyl radicals can lead to different hydroamination products through a mechanism called proton-coupled electron transfer (PCET).* -
  • Cyclic voltammetry analysis showed that the selectivity of the reaction depends on the size of the hydrogen bond complex formed by the carbamate substrate and phosphate base.* -
  • The use of an additive, 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), allows for better control over this selectivity, offering valuable insights for designing redox reaction systems under electrochemical conditions.*

Article Abstract

Electrochemically generated amidyl radical species produced distinct inter- or intramolecular hydroamination reaction products via a proton-coupled electron transfer (PCET) mechanism. Cyclic voltammetry (CV) analysis indicated that the chemoselectivity was derived from the size of the hydrogen bond complex, which consisted of the carbamate substrate and phosphate base, and could be controlled using 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) as an additive. These results provide fundamental insights for the design of PCET-based redox reaction systems under electrochemical conditions.

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Source
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC10877074PMC
http://dx.doi.org/10.3762/bjoc.20.27DOI Listing

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