Typical Metal-Catalyzed Asymmetric Synthesis

不对称合成技术的发展迅速而广泛，在许多情况下，它是一种比酶反应更普遍、更有效的合成光性手性化合物的新方法。“典型金属催化不对称合成”项目的目标是由许多有机化学家组成六个研究小组：“设计师Lewis酸的开发和应用（山本）”、“手性希夫碱-钛配合物催化双烯酮与醛的不对称反应（奥古尼）”、“利用手性季盐催化剂和单萜烯的手性助剂的不对称合成（Shioiri）”、“有机金属基立体控制的一些新方法（铃木）、“不对称分子内氢化反应（Tamao）”和“催化不对称反应的发展（Nakai）”，从1993年开始为期三年。本项目不仅利用典型元素的特性创造了各种新的不对称反应，而且还应用了许多对映和非对映选择反应来合成复杂的多手性化合物，包括有用的天然产物。1993-1995年间，开发了许多新的不对称或立体选择性反应，如diols - alder反应（Yamamoto）、质子化反应（Yamamoto）、二烯酮与醛的加成开环反应（Oguni）、醛醇反应（Shioiri）、硅基乙炔与羰基化合物的加成反应（Shioiri）、炔基1,2重排反应（Suzuki）、金属烯反应（Suzuki）、分子内硅化氢反应（Tamao）、醛基与二乙基锌的加成反应（Nakai）和烯丙基化反应（Nakai）。

Asymmetric synthesis has developed rapidly and extensively, and is now growing into a new way of producing optically active chiral compounds that is more general and efficient than enzymatic reactions in many cases. The aim of project "typical metal-catalyzed asymmetric synthesis, " was executed by many organic chemists diving into six research groups of "development and application of designer Lewis acid (Yamamoto), " "asymmetric reactions of diketene with aldehydes catalyzed by chiral Schiff base-titanium complexes (Oguni), " "asymmetric synthesis utilizing chiral quaternary salt catalysts and chiral auxiliaries from monoterpenes (Shioiri), " "some new ways of organometallicbased stereocontrol (Suzuki), " "asymmetric intramolecular hydrosilation (Tamao), " and "development of catalytic asymmetric reactions (Nakai)" for three years beginning in 1993. This project was not only create various new asymmetric reactions by taking advantage of characteristics of typical elements, but also to apply many enantio- and diastereoselective reactions to the synthesis of the complex multi-chiral compounds including useful natural products. During 1993-1995, many new asymmetric or stereoselective reactions related to Diels-Alder reaction (Yamamoto), protonation (Yamamoto), addition-ring opening reaction of diketenes with aldehydes (Oguni), aldol reaction (Shioiri), addition of silylacetylenes to carbonyl compounds (Shioiri), 1,2-rearrangement of alkynyl groups (Suzuki), metallo-ene reaction (Suzuki), intramolecular hydrosilation (Tamao), addition of aldehydes with diethylzinc (Nakai), and allylation (Nakai) were developed.