Hamada Yasumasa
Graduate School of Pharmaceutical Sciences, Chiba University, Inohana, Chuo-ku, Chiba 260-8675, Japan.
Chem Pharm Bull (Tokyo). 2012;60(1):1-20. doi: 10.1248/cpb.60.1.
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.
2,6-二甲基-9-芳基-9-磷杂双环[3.3.1]壬烷（9-PBN和9-NapBN）以及由天冬氨酸衍生的手性二氨基氧化膦（DIAPHOXs）已分别作为有用的配体和前配体用于过渡金属催化的不对称合成。首次开发了通过动态动力学拆分使用钌、铑、铱和镍催化剂对α-氨基-β-酮酯进行反选择性不对称氢化反应，高效地制备了重要的反式β-羟基-α-氨基酸。通过使用DIAPHOX的过渡金属催化反应、反选择性不对称氢化反应以及我们开发的反应，实现了几种生物活性天然产物的全合成。首次对映选择性地实现了抗肿瘤吲哚生物碱唐古特碱的合成。使用我们开发的不对称串联迈克尔-醛醇反应作为关键步骤，完成了马替林碱手性核心的对映选择性合成。该合成代表了马替林碱和马替林酸的形式全合成。通过使用反选择性不对称氢化反应和我们开发的反应阐明未知立体结构，合成了巴布酰胺B。
