title: β-Amino acid catalyzed asymmetric Michael additions: design of organocatalysts with catalytic acid/base dyad inspired by serine proteases.
abstract: A new type of chiral β-amino acid catalyst has been computationally designed, mimicking the enzyme catalysis of serine proteases. Our catalyst approach is based on the bioinspired catalytic acid/base dyad, namely, a carboxyl and imidazole pair. DFT calculations predict that this designed organocatalyst catalyzes Michael additions of aldehydes to nitroalkenes with excellent enantioselectivities and remarkably high anti diastereoselectivities. The unusual stacked geometry of the enamine intermediate, hydrogen bonding network, and the adoption of an exo transition state are the keys to understand the stereoselectivity.
authors.affiliation: Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543.
authors.forename: Hui
authors.initials: H
authors.lastname: Yang
authors.forename: Ming Wah
authors.initials: MW
authors.lastname: Wong
mesh_terms: D000143:Acids / Q000737:chemistry*; D000468:Alkalies / Q000737:chemistry*; D000596:Amino Acids / Q000737:chemistry*; D002384:Catalysis; D057057:Serine Proteases / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000143:Acids; D000468:Alkalies; D000596:Amino Acids; D057057:Serine Proteases