title: Enantioselective organocatalytic amine conjugate addition.
abstract: The first enantioselective organocatalytic amine conjugate addition has been successfully developed. The application of LUMO-lowering iminium catalysis has enabled the highly chemo- and enantioselective 1,4-addition of a rationally designed N-silyloxycarbamate nucleophile (HOMO-raised) to alpha,beta-unsaturated aldehydes. Imidazolidinone 2*pTSA was found to catalyze the addition of various orthogonally N-protected silyloxycarbamate nucleophiles to a range of alpha,beta-unsaturated aldehydes, affording synthetically useful beta-amino aldehyde intermediates. The synthetic utility of the protocol was demonstrated in the rapid synthesis of enantioenriched beta-amino acids in one operation and 1,3-amino alcohol derivatives in three operations.
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.
authors.forename: Young K
authors.initials: YK
authors.lastname: Chen
authors.forename: Masanori
authors.initials: M
authors.lastname: Yoshida
authors.forename: David W C
authors.initials: DW
authors.lastname: MacMillan
mesh_terms: D000447:Aldehydes / Q000138:chemical synthesis; D000588:Amines / Q000737:chemistry*; D002384:Catalysis; D015394:Molecular Structure
chemical_list: D000447:Aldehydes; D000588:Amines