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Development of Transition-metal Catalysts and Their Applications to Asymmetric Catalysis

过渡金属催化剂的发展及其在不对称催化中的应用

基本信息

批准号：
17390004
负责人：
HAMADA Yasumasa
金额：
$ 9.6万
依托单位：
Chiba University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2005
资助国家：
日本
起止时间：
2005 至 2006
项目状态：
已结题

项目摘要

Development of environmentally-benign processes is most important and challenging task in the 21^<st> century. In our efforts directed towards this task, we have succeeded in development of highly stereoselective catalytic asymmetric syntheses.1.Highly enantio- and diastereoselective hydrogenation of α-amino-β-keto estersRecently, we have demonstrated that α-amino-β-keto esters have been directly hydrogenated in an anti-selective manner with ruthenium-BINAP catalyst to provide β-hydroxy-α-amino acid esters. From further investigation on this hydrogenation, we have found that iridium-axially chiral phosphine also hydrogenates α-amino-β-keto esters to afford efficiently the β-hydroxy-α-amino acid esters.2.Catalytic asymmetric synthesis using chiral diaminophosphine oxidesTransition metal-catalyzed reaction using secondary phosphine oxides or their equivalent have attracted attention in these past several years due to the air and moisture stability of pentavalent phosphine oxides. We succeeded in development of P-chiragenic phosphine oxides based on a chiral diamine framework : aspartic acid-derived P-chirogenic DIAPHOXs. These pentavalent phosphorus compounds, the preligands, reacted with BSA to provide the trivalent diaminophosphite species, which functioned as the actual ligands. With use of the Pd-DIAPHOX catalyst system, asymmetric allylic alkylation, asymmetric allylic amination, and enantioselective construction of quaternary carbons have been achieved.

发展对环境无害的工艺是21世纪最重要和最具挑战性的任务。在我们针对这项任务的努力中，我们已经成功地开发了高度立体选择性的催化不对称合成。α-氨基-β-酮酯的高对映选择性和非对映选择性加氢最近，我们证明了α-氨基-β-酮酯在钌- binap催化剂下以反选择性的方式直接加氢得到β-羟基-α-氨基酸酯。通过进一步研究，我们发现轴向手性膦还能氢化α-氨基-β-酮酯，有效地生成β-羟基-α-氨基酸酯。手性二氨基膦氧化物催化不对称合成由于五价膦氧化物在空气和水分方面的稳定性，近年来以二氨基膦氧化物或其等价物为催化剂的过渡金属催化反应引起了人们的广泛关注。我们成功地开发了基于手性二胺框架的p -手性膦氧化物：天冬氨酸衍生的p -手性DIAPHOXs。这些五价磷化合物，即预配体，与牛血清白蛋白反应生成三价二亚磷酸酯，作为实际的配体。利用Pd-DIAPHOX催化剂体系，实现了不对称烯丙基烷基化、不对称烯丙基胺化和对映选择性构建季碳。