Issue 15, 2021

Photoactive electron donor–acceptor complex platform for Ni-mediated C(sp3)–C(sp2) bond formation

Abstract

A dual photochemical/nickel-mediated decarboxylative strategy for the assembly of C(sp3)–C(sp2) linkages is disclosed. Under light irradiation at 390 nm, commercially available and inexpensive Hantzsch ester (HE) functions as a potent organic photoreductant to deliver catalytically active Ni(0) species through single-electron transfer (SET) manifolds. As part of its dual role, the Hantzsch ester effects a decarboxylative-based radical generation through electron donor–acceptor (EDA) complex activation. This homogeneous, net-reductive platform bypasses the need for exogenous photocatalysts, stoichiometric metal reductants, and additives. Under this cross-electrophile paradigm, the coupling of diverse C(sp3)-centered radical architectures (including primary, secondary, stabilized benzylic, α-oxy, and α-amino systems) with (hetero)aryl bromides has been accomplished. The protocol proceeds under mild reaction conditions in the presence of sensitive functional groups and pharmaceutically relevant cores.

Graphical abstract: Photoactive electron donor–acceptor complex platform for Ni-mediated C(sp3)–C(sp2) bond formation

Supplementary files

Article information

Article type
Edge Article
Submitted
16 2 2021
Accepted
04 3 2021
First published
05 3 2021
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2021,12, 5450-5457

Photoactive electron donor–acceptor complex platform for Ni-mediated C(sp3)–C(sp2) bond formation

L. M. Kammer, S. O. Badir, R. Hu and G. A. Molander, Chem. Sci., 2021, 12, 5450 DOI: 10.1039/D1SC00943E

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