Regioselective C−H Xanthylation as a Platform for Polyolefin Functionalization

Polyolefins that contain polar functional groups are important materials for next‐generation lightweight engineering thermoplastics. Post‐polymerization modification is an ideal method for the incorporation of polar groups into branched polyolefins; however, it typically results in chain scission ev...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2018-05, Vol.57 (21), p.6261-6265
Main Authors: Williamson, Jill B., Czaplyski, William L., Alexanian, Erik J., Leibfarth, Frank A.
Format: Article
Language:English
Subjects:
amidyl radicals
Chain branching
Chain scission
Cleavage
C−H functionalization
Functional groups
photochemistry
polymer modification
Polymerization
Polymers
Polyolefins
Regioselectivity
Thermoplastic resins
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Summary:Polyolefins that contain polar functional groups are important materials for next‐generation lightweight engineering thermoplastics. Post‐polymerization modification is an ideal method for the incorporation of polar groups into branched polyolefins; however, it typically results in chain scission events, which have deleterious effects on polymer properties. Herein, we report a metal‐free method for radical‐mediated C−H xanthylation that results in the regioselective functionalization of branched polyolefins without coincident polymer‐chain scission. This method enables a tunable degree of polymer functionalization and capitalizes on the versatility of the xanthate functional group to unlock a wide variety of C−H transformations previously inaccessible on branched polyolefins. Commodity polymers see the light: Functionalized polyolefins were obtained by intermolecular, metal‐free, and regioselective xanthylation without the chain‐scission side reactions that plague current commercial strategies. The method enables a tunable degree of polymer functionalization and capitalizes on the versatility of the xanthate functional group to unlock a wide variety of C−H transformations previously inaccessible on branched polyolefins.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201803020