A General Approach to Site‐Specific, Intramolecular C−H Functionalization Using Dithiocarbamates

Intramolecular hydrogen atom transfer is an established approach for the site‐specific functionalization of unactivated, aliphatic C−H bonds. Transformations using this strategy typically require unstable intermediates formed using strong oxidants and have mainly targeted C−H halogenations or intram...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2018-10, Vol.57 (40), p.13106-13109
Main Authors: Na, Christina G., Alexanian, Erik J.
Format: Article
Language:English
Subjects:
Aliphatic compounds
Bonding strength
Carbamates - chemistry
Carbon - chemistry
C−H functionalization
Hydrogen - chemistry
hydrogen atom transfer
Intermediates
Light
Oxidants
Oxidizing agents
radical reactions
regioselectivity
Sulfhydryl Compounds - chemistry
synthetic methods
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Summary:Intramolecular hydrogen atom transfer is an established approach for the site‐specific functionalization of unactivated, aliphatic C−H bonds. Transformations using this strategy typically require unstable intermediates formed using strong oxidants and have mainly targeted C−H halogenations or intramolecular aminations. Herein, we report a site‐specific C−H functionalization that significantly increases the synthetic scope and convergency of reactions proceeding via intramolecular hydrogen atom transfer. Stable, isolable N‐dithiocarbamates are used as precursors to amidyl radicals formed via either light or radical initiation to efficiently deliver highly versatile alkyl dithiocarbamates across a wide range of complex structures. Smart up your HAT: A site‐specific C−H functionalization is presented that significantly increases the synthetic scope and convergency of reactions proceeding via intramolecular hydrogen atom transfer. Stable, isolable dithiocarbamates are used as precursors to amidyl radicals formed via either light or radical initiation to efficiently deliver highly versatile alkyl dithiocarbamates across a wide range of complex structures.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201806963