Issue 19, 2018

β C–H di-halogenation via iterative hydrogen atom transfer


A radical relay strategy for mono- and di-halogenation (iodination, bromination, and chlorination) of sp3 C–H bonds has been developed. This first example of β C–H di-halogenation is achieved through sequential C–H abstraction by iterative, hydrogen atom transfer (HAT). A double C–H functionalization is enabled by in situ generated imidate radicals, which facilitate selective N˙ to C˙ radical translocation and tunable C–X termination. The versatile, geminal di-iodide products are further elaborated to β ketones and vinyl iodides. Mechanistic experiments explain the unique di-functionalization selectivity of this iterative HAT pathway, wherein the second C–H iodination is twice as fast as the first.

Graphical abstract: β C–H di-halogenation via iterative hydrogen atom transfer

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Article information

Article type
Edge Article
14 Mar 2018
19 Apr 2018
First published
30 Apr 2018
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2018,9, 4500-4504

β C–H di-halogenation via iterative hydrogen atom transfer

E. A. Wappes, A. Vanitcha and D. A. Nagib, Chem. Sci., 2018, 9, 4500 DOI: 10.1039/C8SC01214H

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