Photochemical benzylic radical arylation promoted by supported Pd nanostructures

Gawargy, Teresa A.; Costa, Paolo; Lanterna, Anabel E.; Scaiano, Juan C.

Abstract

We report a novel way to promote photochemical benzylic radical arylations using Pd nanostructures. Traditional benzylic radical reaction pathways are challenged by the presence of metal centres that provoke unprecedented regioselectivity towards more synthetically relevant C(sp3)-C(sp2) couplings. This new C-H activation pathway is rationalised by means of a pseudo-persistent radical effect facilitated by metal centres. We show the mechanistic and computational aspects of the heterogeneous photocatalytic processes that are the root of this drastic change in reactivity.

• Journal Article Type: Article
• Acceptance Date: Jul 15, 2020
• Online Publication Date: Jul 16, 2020
• Publication Date: Aug 21, 2020
• Deposit Date: Jul 21, 2020
• Publicly Available Date: Jul 17, 2021
• Journal: Organic and Biomolecular Chemistry
• Print ISSN: 1477-0520
• Electronic ISSN: 1477-0539
• Peer Reviewed: Peer Reviewed
• Volume: 18
• Issue: 31
• Pages: 6047-6052
• DOI: https://doi.org/10.1039/d0ob01227k
• Keywords: Physical and Theoretical Chemistry; Organic Chemistry; Biochemistry
• Public URL: https://nottingham-repository.worktribe.com/output/4780000
• Publisher URL: https://pubs.rsc.org/en/Content/ArticleLanding/2020/OB/D0OB01227K#!divAbstract
• Additional Information: : This document is Similarity Check deposited; : Supplementary Information; : Single-blind; : Received 15 June 2020; Accepted 15 July 2020; Accepted Manuscript published 16 July 2020