This review presents examples from the chemical literature of syntheses of bridged-polycyclic products via C-H bond insertion by carbenes and nitrenes. Applications to natural product synthesis, a description of the essential elements in substrate-controlled reactions, and mechanistic details of transformations are presented. Overall, these transformations allow the construction of important ri...

A new class of enantiopure carbene precursors based on cheap camphor has been developed, and a restricted rotation of one N-substituent due to the C-10 methyl group of the camphor skeleton has been found; in situ prepared corresponding carbenes revealed the same behaviour.

A theoretical study focusing on the ring expansion that occurs in the reaction of N-heterocyclic carbenes with silanes has been carried out. A detailed reaction pathway was determined which indicates that formation of C-H bonds is the crucial factor in the transformation.

N-Heterocyclic carbenes catalyzed hydrophosphonylation reaction of α-ketoesters and α-trifluoromethyl ketones was developed. Under the catalysis of 10 mol% IPr, α-ketoesters or α-trifluoromethyl ketones reacted with dialkyl phosphites to provide quaternary α-hydroxyphosphonates in good to excellent yield.

The geometries and relative stabilities of the singlet and triplet states of phenyl- (Cs), diphenyl- (C2), 1-naphthyl- (Cs), di(1-naphthyl)- (C2), and 9-anthryl-substituted (Cs) carbenes were investigated at the B3LYP/6-311+G(d,p) + ZPVE level of density functional theory. The singlet-triplet energy separations (DeltaEST), 2.7, 2.9, 3.4, 3.7, and 5.7 kcal/mol, respectively, after including an e...

Discovered in 2005, cyclic (alkyl)(amino)carbenes (CAACs) have led to numerous discoveries the field of ruthenium olefin metathesis, until then largely dominated by well-known N-heterocyclic...

The conjugate acids of 1,2,3-triazolylidene mesoionic carbenes can be prepared in a straightforward fashion by alkylation 1-substituted 1,2,3-triazoles. However, this becomes much more challen...