In contrast to alcohols and amines, racemic lactams and thiolactams cannot be resolved directly via enzymatic acylation or classical resolution. Asymmetric N-acylation promoted by amidine-based catalysts, particularly Cl-PIQ 2 and BTM 3, provides a convenient method for the kinetic resolution of these valuable compounds and often achieves excellent levels of enantioselectivity in this process. Density functional theory calculations indicate that the reaction occurs via N-acylation of the lactim tautomer and that cation-π interactions play a key role in the chiral recognition of lactam substrates.

The reaction of S-2-bromophenyl-S-methylsulfoximine with terminal alkynes in the presence of a palladium catalyst resulted in the formation of both 1,2-benzothiazines and 1,2-benzoisothiazoles. A preference for the former was seen with alkylalkynes, while the latter were preferentially formed with alkynylarenes.

Methanolysis of N-acyl-thiazolidin-2-thiones and -oxazolidin-2-thiones in the presence of acyl transfer catalyst benzotetramisole (BTM) proceeds in a highly enantioselective fashion thus enabling kinetic resolution of these substrates.

Enantioselective N-acylation of 4-aryl-β-lactams in the presence of acyl transfer catalyst Cl-PIQ provides an effective method for their non-enzymatic kinetic resolution.

The first nonenzymatic kinetic resolution of β-lactams has been achieved. Alcoholysis of their N-aroyl derivatives in the presence of a simple chiral acyl transfer catalyst, benzotetramisole, produces β-amino acid derivatives with excellent enantioselectivity.