title: Preparation of Enantiomerically Pure Perfluorobutanesulfinamide and Its Application to the Asymmetric Synthesis of α-Amino Acids.
abstract: A high yielding and practical two-step synthesis of enantiomerically pure perfluorobutanesulfinamide from Senanayake's 2-aminoindanol-derived sulfinyl transfer reagent was developed and carried out on a multigram scale. Straightforward condensation of this sulfinamide with ethyl glyoxylate provided the N-perfluorobutanesulfinyl imino ester. The utility of this activated N-sulfinyl imino ester was demonstrated for reactions that gave either no product or very low yields with the corresponding less electrophilic N-tert-butanesulfinyl derivative. Specifically, the Rh(III)-catalyzed C-H bond addition of aromatic compounds to the N-perfluorobutanesulfinyl imino ester provided arylglycines with very high diastereoselectivities for a range of directing groups including pyrrolidine amide, azo, sulfoximine, 1-pyrazole, and 1,2,3-triazole functionalities. Thermal asymmetric aza-Diels-Alder reactions also proceeded in good yields and with high selectivity, including for the substituted dienes (E)-1,3-pentadiene and (2E,4E)-2,4-hexadiene.
authors: Department of Chemistry, Yale University , 225 Prospect Street, New Haven, Connecticut 06520-8170, United States.
authors: Apiwat
authors: A
authors: Wangweerawong
authors: Department of Chemistry, Yale University , 225 Prospect Street, New Haven, Connecticut 06520-8170, United States.
authors: Joshua R
authors: JR
authors: Hummel
authors: Division of Chemical Sciences, Lawrence Berkeley National Laboratory, and Department of Chemistry, University of California , Berkeley, California 94720, United States.
authors: Robert G
authors: RG
authors: Bergman
authors: Department of Chemistry, Yale University , 225 Prospect Street, New Haven, Connecticut 06520-8170, United States.
authors: Jonathan A
authors: JA
authors: Ellman
mesh_terms: D000466:Alkadienes / Q000737:chemistry*; D000596:Amino Acids / Q000138:chemical synthesis* / Q000737:chemistry; D003500:Cyclization; D015394:Molecular Structure; D013237:Stereoisomerism; D013449:Sulfonamides / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D000466:Alkadienes; D000596:Amino Acids; D013449:Sulfonamides