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 feb 2021
Accepted
04 mar 2021
First published
05 mar 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

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements