Synthesis of a Tertiary Carbinamide via a Novel Rh-Catalyzed Asymmetric Hydrogenation

• Published in: Journal of organic chemistry Vol. 73; no. 4; pp. 1639 - 1642
• Main Authors: Limanto, John, Shultz, C. Scott, Dorner, Benjamin, Desmond, Richard A, Devine, Paul N, Krska, Shane W
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 15.02.2008; Amer Chemical Soc
• Subjects: Amides - chemistry; Catalysis; Chemistry; Chemistry, Organic; Crystallization; Exact sciences and technology; Heterocyclic compounds; Heterocyclic compounds with only one n hetero atom and condensed derivatives; Hydrogen - chemistry; Magnetic Resonance Spectroscopy; Organic chemistry; Physical Sciences; Preparations and properties; Rhenium - chemistry; Science & Technology; Spectrophotometry, Infrared; GROWTH-HORMONE SECRETAGOGUES; DESIGN; REAGENTS; MECHANISM; LIGANDS; ACIDS; ENANTIOSELECTIVE HYDROGENATION; 1-TETRALONES; 1-INDANONES; Rhodium complex; Catalytic reaction; Rhodium I; Nitrogen heterocycle; Crystallization; Hydrogenation; Tetrahydrofurane; Allylic compound; Spiran; Asymmetric synthesis; Carboxamide; Cations; Chemical synthesis
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo702429u

Asymmetric hydrogenation of allylic dimethylcarbinamide 2 with 1 mol % of cationic Rh(I)−Josiphos complex in THF under 500 psi of H2 generated the corresponding tertiary carbinamide 1 in 98.5% assay yield and a 94:6 enantiomeric ratio. Upon crystallization, the product was isolated in 91% isolated yield and 95:5 enantiomeric ratio.