Development of new methods in organic synthesis and their applications to the synthesis of biologically interesting natural products.
2,6-Dimethyl-9-Aryl-9-phosphabicyclo[3.3.1]nonanes (9-PBN and 9-NapBN) and the chiral diaminophosphine oxides (DIAPHOXs) derived from aspartic acid have been introduced as useful ligands and preligands, respectively, for transition metal-catalyzed asymmetric synthesis. anti-Selective asymmetric hydrogenation of α-amino-β-ketoesters using Ru-, Rh-, Ir-, and Ni-catalysts through dynamic kinetic resolution have been developed for the first time, producing efficiently important anti β-hydroxy-α-amino acids. The total synthesis of several biologically active natural products was achieved by use of the transition metal-catalyzed reaction using DIAPHOX, anti-selective asymmetric hydrogenation, and reactions developed by us. Synthesis of tangutorine, an antitumor indole alkaloid, has been enantioselectively achieved for the first time. Enantioselective synthesis of a martinelline chiral core was accomplished using the asymmetric tandem Michael-Aldol reaction as a key step developed by us. This synthesis represents the formal total synthesis of martinelline and martinellic acid. Papuamide B was synthesized through the elucidation of unknown stereostructures by using the anti-selective asymmetric hydrogenation and reactions developed by us.
Graduate School of Pharmaceutical Sciences, Chiba University, Inohana, Chuo-ku, Chiba 260-8675, Japan.
Yasumasa
Y
Hamada
D000970:Antineoplastic Agents / Q000138:chemical synthesis / Q000737:chemistry; D001688:Biological Products / Q000138:chemical synthesis / Q000737:chemistry*; D001643:Bridged Bicyclo Compounds / Q000138:chemical synthesis / Q000737:chemistry; D002384:Catalysis; D010720:Phosphines / Q000737:chemistry; D013237:Stereoisomerism; D028561:Transition Elements / Q000737:chemistry
D000970:Antineoplastic Agents; D001688:Biological Products; D001643:Bridged Bicyclo Compounds; D010720:Phosphines; D028561:Transition Elements; C458301:bicyclo(3.3.1)nonane; C044646:phosphine