Catalytic, Enantioselective Alkylation of α-Imino Esters: The Synthesis of Nonnatural α-Amino Acid Derivatives
- 4 December 2001
- journal article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 124 (1) , 67-77
- https://doi.org/10.1021/ja016838j
Abstract
Methodology for the practical synthesis of nonnatural amino acids has been developed through the catalytic, asymmetric alkylation of α-imino esters and N,O-acetals by enol silanes, ketene acetals, alkenes, and allylsilanes using chiral transition metal-phosphine complexes as catalysts (1−5 mol %). The alkylation products, which are prepared with high enantioselectivity (up to 99% ee) and diastereoselectivity (up to 25:1/anti:syn), are protected nonnatural amino acids that represent potential precursors to natural products and pharmaceuticals. A kinetic analysis of the catalyzed reaction of alkenes with α-imino esters is presented to shed light on the mechanism of this reaction.Keywords
This publication has 77 references indexed in Scilit:
- Recent Developments in Catalytic Asymmetric Strecker-Type ReactionsAngewandte Chemie International Edition in English, 2001
- Formation of Optically Active Aromaticα-Amino Acids by Catalytic Enantioselective Addition of Imines to Aromatic CompoundsPublished by Wiley ,2000
- Catalytic Asymmetric Hetero-Diels–Alder Reactions of Carbonyl Compounds and IminesPublished by Wiley ,2000
- Ti-Catalyzed Regio- and Enantioselective Synthesis of Unsaturated α-Amino Nitriles, Amides, and Acids. Catalyst Identification through Screening of Parallel LibrariesJournal of the American Chemical Society, 2000
- Mechanism of Palladium Complex-Catalyzed Enantioselective Mannich-Type Reaction: Characterization of A Novel Binuclear Palladium Enolate ComplexJournal of the American Chemical Society, 1999
- Apparent Catalytic Generation of Chiral Metal Enolates: Enantioselective Dienolate Additions to Aldehydes Mediated by Tol-BINAP·Cu(II) Fluoride ComplexesJournal of the American Chemical Society, 1998
- Chemistry of O-Silylated Ketene Acetals: A Stereoselective Synthesis of Optically Active Carbapenem Antibiotics, (+)-Thienamycin and (+)-PS-5.CHEMICAL & PHARMACEUTICAL BULLETIN, 1992
- Asymmetric glyoxylate-ene reaction catalyzed by chiral titanium complexes: a practical access to .alpha.-hydroxy esters in high enantiomeric puritiesJournal of the American Chemical Society, 1989
- Copper(I) complexes with bidentate tertiary phosphine ligands: solution chemistry and antitumor activityInorganic Chemistry, 1987
- A Rate Study of the Silanol Condensation Reaction at 25° in Alcoholic Solvents1Journal of the American Chemical Society, 1954