Work

Sulfamate Esters Guide Selective Radical‐Mediated Chlorination of Aliphatic C−H Bonds

Year: 2017

Type: article

Abstract: Masked alcohols are particularly appealing as directing groups because of the ubiquity of hydroxy groups in organic small molecules. Herein, we disclose a general strategy for aliphatic γ‐C(sp 3 )−H functionalization guided by a masked alcohol. Specifically, we determine that sulfamate ester derived nitrogen‐centered radicals mediate 1,6‐hydrogen‐atom transfer (HAT) processes to guide γ‐C(sp 3 )−H chlorination. This reaction proceeds through a light‐initiated radical chain‐propagation process and is capable of installing chlorine atoms at primary, secondary, and tertiary centers.

Source: Angewandte Chemie International Edition

DOI: 10.1002/anie.201710322

Authors: Melanie A. Short, J. Miles Blackburn, Jennifer L. Roizen

Institution: Duke University

Language: English

Topic: Radical Photochemical Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: American Chemical Society Petroleum Research Fund, National Institute of General Medical Sciences, Division of Chemistry

Awards: Pharmacological Sciences Training Grant, G5833396658, G6062378115, G8190612876