Tertiary‐Alcohol‐Directed Functionalization of Remote C(sp3)−H Bonds by Sequential Hydrogen Atom and Heteroaryl Migrations. Issue 6 (12th January 2018)

• Record Type: Journal Article
• Authors: Wu, Xinxin; Wang, Mingyang; Huan, Leitao; Wang, Dongping; Wang, Jinwei; Zhu, Chen
• Is Part Of: Angewandte Chemie international edition. Volume 57:Issue 6(2018)
• Page Start: 1640
• Page End: 1644
• Publication Date: 2018-01-12
• Subjects: C−H activation -- electron transfer -- heteroaryls -- photocatalysis -- radicals; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201709025
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Reported for the first time is a tertiary‐alcohol‐guided heteroarylation of remote C(sp 3 )−H bonds. The mild and direct generation of alkoxyl radicals from alcohols is enabled by visible‐light photocatalysis. A remote hydrogen atom and heteroaryl migration sequence are involved in the reaction. Many sensitive groups remain intact in the reaction, thus illustrating wide functional‐group compatibility. This protocol provides a practical strategy for the late‐stage modification of alkyl ketones. Abstract : Smart migration : A new method, the tertiary‐alcohol‐directed functionalization of remote C(sp 3 )−H bonds, is disclosed. The mild generation of the alkoxyl radical from the alcohol O−H bond under visible‐light photocatalysis is noteworthy and enables the hydrogen atom and heteroaryl group migration sequence. This method provides a practical strategy for the late‐stage modification of alkyl ketones. HAT=hydrogen‐atom transfer.