Copper-promoted site-selective carbonylation of sp3 and sp2 C–H bonds with nitromethane. Issue 8 (11th May 2016)

• Record Type: Journal Article
• Authors: Wu, Xuesong; Miao, Jinmin; Li, Yanrong; Li, Guigen; Ge, Haibo
• Is Part Of: Chemical science. Volume 7:Issue 8(2016:Aug.)
• Page Start: 5260
• Page End: 5264
• Publication Date: 2016-05-11
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/c6sc01087c
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : A copper-promoted site-selective carbonylation of sp 2 and sp 3 C–H bonds with nitromethane as an unprecedented source of carbonyl carbon is described. Abstract : Copper-promoted direct carbonylation of unactivated sp 3 C–H and aromatic sp 2 C–H bonds of amides was developed using nitromethane as a novel carbonyl source. The sp 3 C–H functionalization showed high site-selectivity by favoring the C–H bonds of α-methyl groups. The sp 2 C–H carbonylation featured high regioselectivity and good functional group compatibility. Kinetic isotope effect studies indicated that the sp 3 C–H bond breaking step is reversible, whereas the sp 2 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.