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

Kazuhiro Okamoto; Naoki Shida; Mahito Atobe

doi:10.3762/bjoc.20.27

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

Beilstein J Org Chem. 2024 Feb 12:20:264-271. doi: 10.3762/bjoc.20.27. eCollection 2024.

Authors

Kazuhiro Okamoto¹, Naoki Shida¹, Mahito Atobe¹

Affiliation

¹ Graduate School of Engineering, Yokohama National University, 79-7 Tokiwadai, Hodogaya-ku, Yokohama, Kanagawa 240-8501, Japan.

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.

Keywords: amidyl radical; cyclic voltammetry; electrosynthesis; hydroamination; proton coupled electron transfer.

Grants and funding

This work was supported by JSPS KAKENHI (Grant Nos. 22K18915 and 21H05215 to M.A. and 22H02118 23K17370, and 23H04916 to N.S.), a Grant-in-Aid for JSPS Fellows (Grant No. 22J00431 to K.O.), and JST CREST (Grant No. 18070940 to M.A.).