Photocatalytic Strategy for Decyanative Transformations Enabled by Amine-Ligated Boryl Radical

Yuto Yoshida; Waka Okada; Kazutake Takada; Shuichi Nakamura; Naoki Yasukawa

doi:10.1021/acs.orglett.4c04701

Photocatalytic Strategy for Decyanative Transformations Enabled by Amine-Ligated Boryl Radical

Org Lett. 2025 Jan 10. doi: 10.1021/acs.orglett.4c04701. Online ahead of print.

Authors

Yuto Yoshida¹, Waka Okada¹, Kazutake Takada¹, Shuichi Nakamura¹, Naoki Yasukawa¹

Affiliation

¹ Department of Life Science and Applied Chemistry, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555, Japan.

PMID: 39792938
DOI: 10.1021/acs.orglett.4c04701

Abstract

Decyanation after α-functionalization by exploiting the inherent properties of cyano groups enables the strategic assembly of a carbon scaffold. Herein, we demonstrate an amine-ligated boryl radical-mediated cyano group transfer (CGT) strategy of malononitriles under photocatalytic conditions. This strategy allows for the cleavage of C(sp³)-CN and the formation of C(sp³)-D and C(sp³) to realize decyanative deuteration and cyclization via radical-polar crossover. Computational studies successfully demonstrated the reactivity of CGT promoters can be accurately assessed.