Sulfamate Esters Guide Selective Radical‐Mediated Chlorination of Aliphatic C−H Bonds |
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Authors: | Melanie A. Short J. Miles Blackburn Prof. Dr. Jennifer L. Roizen |
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Affiliation: | Duke University, Department of Chemistry, Box 90346, Durham, NC, USA |
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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(sp3)?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(sp3)?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. |
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Keywords: | chlorination directing groups halogenation hydrogen transfer radical reactions |
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