Work

O–H hydrogen bonding promotes H-atom transfer from α C–H bonds for C-alkylation of alcohols

Year: 2015

Type: article

Abstract: The efficiency and selectivity of hydrogen atom transfer from organic molecules are often difficult to control in the presence of multiple potential hydrogen atom donors and acceptors. Here, we describe the mechanistic evaluation of a mode of catalytic activation that accomplishes the highly selective photoredox α-alkylation/lactonization of alcohols with methyl acrylate via a hydrogen atom transfer mechanism. Our studies indicate a particular role of tetra-n-butylammonium phosphate in enhancing the selectivity for α C-H bonds in alcohols in the presence of allylic, benzylic, α-C=O, and α-ether C-H bonds.

Source: Science

DOI: 10.1126/science.aac8555

Authors: Jenna L. Jeffrey, Jack A. Terrett, David W. C. MacMillan

Institution: Princeton University

Language: English

Topic: Radical Photochemical Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: Amgen, Bristol-Myers Squibb, National Institutes of Health, National Institute of General Medical Sciences

Awards: Photoredox Catalysis Applications in Organometallics and Chemical Biology, G1588828791, G30908861, Beta Functionalization of Aldehydes and Ketones Using Photoredox Organocatalysis