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Sulfamate Esters Guide Selective Radical-Mediated Chlorination of Aliphatic C-H Bonds.

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 ?-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 ?-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.

SUBMITTER: Short MA

PROVIDER: S-EPMC5745255 | biostudies-literature | 2018 Jan

REPOSITORIES: biostudies-literature

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Sulfamate Esters Guide Selective Radical-Mediated Chlorination of Aliphatic C-H Bonds.

Short Melanie A MA Blackburn J Miles JM Roizen Jennifer L JL

Angewandte Chemie (International ed. in English) 20171207 1

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-pr ...[more]

PMID: 29096044

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