Direct Aerobic Carbonylation of C(sp²)–H and C(sp³)–H Bonds through Ni/Cu Synergistic Catalysis with DMF as the Carbonyl Source

Abstract

The direct carbonylation of aromatic sp(2) and unactivated sp(3) C-H bonds of amides was achieved via nickel/copper catalysis under atmospheric O2 with the assistance of a bidentate directing group. The sp(2) C-H functionalization showed high regioselectivity and good functional group compatibility. The sp(3) C-H functionalization showed high site-selectivity by favoring the C-H bonds of α-methyl groups over those of the α-methylene, β- or γ-methyl groups. Moreover, this reaction showed a predominant preference for functionalizing the α-methyl over α-phenyl group. Mechanistic studies revealed that nickel/copper synergistic catalysis is involved in this process.

Recent Advances in First‐Row‐Transition‐Metal‐Catalyzed Dehydrogenative Cou­pling of C(sp3)–H Bonds

“…[30] Succinimide derivatives were prepared from corresponding aromatic or aliphatic amides with 10 mol-% of a Ni I salt and 20 mol-% Cu(acac) 2 in the presence of DMF under oxygen gas. For reactions of aliphatic amides, a predominant preference of functionalizing the methyl group over the methylene groups including the relatively reactive benzyl group was observed.…”

Nickel-Catalyzed C–H Bond Functionalization Utilizing an N,N′-Bidentate Directing Group

“…Ge recently reported on the Ni(II)/Cu(II)-catalyzed carbonylation of benzamides containing an 8-aminoquinoline as the directing group with DMF as the carbonyl source (Scheme 15) [42]. The presence of both a Ni and a Cu catalyst was required for the reaction to proceed.…”

“…Ge reported on the Ni(II)/Cu(II)-catalyzed carbonylation of C(sp 2 )-H bonds in aromatic amides containing an 8-aminoquinoline as the directing group with DMF as the carbonyl source (Scheme 15) [42]. This catalytic system was applicable to the carbonylation of C(sp 3 )-H bonds (Scheme 25) [42].…”

“…This catalytic system was applicable to the carbonylation of C(sp 3 )-H bonds (Scheme 25) [42]. A quaternary α-carbon to the carbonyl group in the substrates is required for the carbonylation to proceed.…”

Pd/C-catalyzed carbonylative C–H activation with DMF as the CO source

“…[8] More recently, Ge and co-workers demonstrated that the methyl group from DMF can service as a carbonyl source on nickel-catalyzed carbonylative C-H activation. [9] Based on our continual interests on carbonylation transformations, [10] here we wish to report our new finding on using the carbonyl part of DMF as the CO source for Pd/Ccarbonylative C-H activation.…”