Synthesis of a tertiary carbinamide via a novel Rh-catalyzed asymmetric hydrogenation.
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.
Limanto
John
J
Department of Process Research, Merck Research Laboratories, Merck & Co., Inc., Rahway, New Jersey 07065, USA. john_limanto@merck.com
Shultz
C Scott
CS
Dorner
Benjamin
B
Desmond
Richard A
RA
Devine
Paul N
PN
Krska
Shane W
SW
D000577:Amides / Q000737:chemistry*; D002384:Catalysis; D003460:Crystallization; D006859:Hydrogen / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D012211:Rhenium / Q000737:chemistry*; D013055:Spectrophotometry, Infrared
D000577:Amides; D012211:Rhenium; D006859:Hydrogen