Masami Kuriyama

Chiral amidomonophosphine-rhodium(I) catalyst for asymmetric 1,4-addition of arylboronic acids to cycloalkenones

Abstract The asymmetric 1,4-addition reaction of arylboronic acids with cycloalkenones was catalyzed by 1 mol% of an amidomonophosphine-rhodium(I) catalyst in a 10:1 mixture of dioxane and water at 100°C, affording 3-arylcycloalkanones in reasonably high enantioselectivity (up to 96% ee) and high yields (up to 99%). The reaction efficacy of phenylboronic acid with cyclohex-2-enone was significantly dependent on the initiation procedure when BINAP was used as a phosphine.

Steric Tuning of the Amidomonophosphane-Rhodium(I) Catalyst in Asymmetric Addition of Arylboroxines to N-Phosphinoyl Aldimines

Highly enantioselective rhodium-catalyzed addition of arylboroxines to N-phosphinoylaldimines was realized by the steric tuning of a diphenylphosphorus moiety to a di(o-tolyl)phosphorus moiety of a chiral amidomonophosphane. The presence of MS 4 A in a 5:1 solvent mixture of dioxane-propanol was essential to afford the corresponding diarylmethylamines in high yield.

The first asymmetric synthesis of a dopamine D1 agonist, dihydrexidine, employing asymmetric conjugate addition technology

Abstract The first asymmetric synthesis of benzophenanthridine dopamine D1 full agonist, dihydrexidine, was accomplished employing three key processes, external chiral ligand-controlled conjugate addition of phenyllithium, Curtius conversion of a carboxylic group to an amino group, and finally Pictet–Spengler type cyclization completing skeleton construction.

Rhodium-catalyzed asymmetric phenylation of N-phosphinoylarylimines with triphenylborane

Triphenylborane asymmetrically transfers its phenyl group to N-diphenylphosphinoylarylimines to give diarylmethylamines with high ee in high yield without imine hydrolysis under the catalysis of a chiral amidomonophosphane–rhodium(I) complex.