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Sulfamate Esters Guide Selective Radical‐Mediated Chlorination of Aliphatic C−H Bonds
Author(s) -
Short Melanie A.,
Blackburn J. Miles,
Roizen Jennifer L.
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201710322
Subject(s) - chemistry , radical , surface modification , primary (astronomy) , alcohol , molecule , chlorine atom , chlorine , hydrogen atom , photochemistry , hydrogen bond , nitrogen , organic chemistry , nitrogen atom , combinatorial chemistry , medicinal chemistry , group (periodic table) , astronomy , physics
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.