Amination of Diazocarbonyl Compounds: N–H Insertion under Metal-Free Conditions

Abstract

Transition-metal-free intermolecular N-H insertion of α-diazocarbonyl compounds is reported. Among the series of nitrogen sources examined, dibenzenesulfonimide was found to be the choice in terms of the yields and the reaction time. Primary mechanistic experiments suggest that a pathway involving a sequence of protonation and nucleophilic substitution was preferred.

TBAI-Catalyzed S–H and N–H Insertion Reactions of α-Diazoesters with Thiophenols and Amines under Metal-Free Conditions

“…Further, a catalyst-free, thermally induced N–H insertion of donor/acceptor carbenes has been disclosed by the group of Davies . Huang and co-workers have developed an efficient catalyst-free N–H bond insertion of α-diazo compounds under mild conditions . More recently, photoinduced photolysis reactions with diazo compounds have emerged as a rapidly growing field in organic synthesis (Scheme b) .…”

Catalyst‐Free S–S Bond Insertion Reaction of a Donor/Acceptor‐Free Carbene by a Radical Process: A Combined Experimental and Computational Study

“…In addition, we found that the optimized reaction conditions were also compatible with the S–H bond insertion reaction of a D/A‐free carbene and gave the sulfur ethers in excellent yields [Equation (6)]. Metal‐catalyzed S–H insertion with phenyl diazoester have long been known; however, this is the only example under thermal conditions to give the insertion product 7 in high yields with high selectivity …”

Palladium-Catalyzed Three-Component Selective Aminoallylation of Diazo Compounds

“…To our knowledge, palladium-catalyzed three-component amination and alkylation of carbenic carbon center, which could lead to fully substituted αamino acid derivatives, is hitherto unknown. In line with our research interests in diazo chemistry [28][29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46][47][48][49][50] , we wonder whether a cascade reaction on amination and allylic alkylation of a transient palladium carbene [51][52][53][54][55][56][57][58][59][60] intermediate could take place. If such a three-componentreaction is feasible, compounds embedded with α,α-disubstituted α-amino acid motif could also prepared in a modular manner 61 (Scheme 1b).…”