Issue 8, 2016

Copper-promoted site-selective carbonylation of sp3 and sp2 C–H bonds with nitromethane

Abstract

Copper-promoted direct carbonylation of unactivated sp3 C–H and aromatic sp2 C–H bonds of amides was developed using nitromethane as a novel carbonyl source. The sp3 C–H functionalization showed high site-selectivity by favoring the C–H bonds of α-methyl groups. The sp2 C–H carbonylation featured high regioselectivity and good functional group compatibility. Kinetic isotope effect studies indicated that the sp3 C–H bond breaking step is reversible, whereas the sp2 C–H bond cleavage is an irreversible but not the rate-determining step. Control experiments showed that a nitromethyl intermediate should be involved in the present reaction.

Graphical abstract: Copper-promoted site-selective carbonylation of sp3 and sp2 C–H bonds with nitromethane

Supplementary files

Article information

Article type
Edge Article
Submitted
08 Mar 2016
Accepted
26 Apr 2016
First published
26 Apr 2016
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., 2016,7, 5260-5264

Copper-promoted site-selective carbonylation of sp3 and sp2 C–H bonds with nitromethane

X. Wu, J. Miao, Y. Li, G. Li and H. Ge, Chem. Sci., 2016, 7, 5260 DOI: 10.1039/C6SC01087C

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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