title: Catalytic, enantioselective N-acylation of lactams and thiolactams using amidine-based catalysts.
abstract: 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.
authors.affiliation: Department of Chemistry, Washington University, One Brookings Drive, St. Louis, Missouri 63130, USA.
authors.forename: Xing
authors.initials: X
authors.lastname: Yang
authors.forename: Valentina D
authors.initials: VD
authors.lastname: Bumbu
authors.forename: Peng
authors.initials: P
authors.lastname: Liu
authors.forename: Ximin
authors.initials: X
authors.lastname: Li
authors.forename: Hui
authors.initials: H
authors.lastname: Jiang
authors.forename: Eric W
authors.initials: EW
authors.lastname: Uffman
authors.forename: Lei
authors.initials: L
authors.lastname: Guo
authors.forename: Wei
authors.initials: W
authors.lastname: Zhang
authors.forename: Xuntian
authors.initials: X
authors.lastname: Jiang
authors.forename: K N
authors.initials: KN
authors.lastname: Houk
authors.forename: Vladimir B
authors.initials: VB
authors.lastname: Birman
mesh_terms: D000215:Acylation; D000578:Amidines / Q000737:chemistry*; D002384:Catalysis; D007769:Lactams / Q000138:chemical synthesis* / Q000737:chemistry*; D015394:Molecular Structure; D011789:Quantum Theory; D013237:Stereoisomerism
chemical_list: D000578:Amidines; D007769:Lactams