Typical Metal-Catalyzed Asymmetric Synthesis

不对称合成反应发展迅速，现已成为一种比酶促反应更普遍、更有效的制备光学活性手性化合物的新方法。“典型的金属催化不对称合成“项目是由多位有机化学家组成的“设计师刘易斯酸的开发与应用”六个研究小组共同完成的（Yamamoto），““通过手性席夫碱-钛络合物催化的双烯酮与醛的不对称反应（Oguni），““利用手性季盐催化剂和来自单萜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“、“不对称分子内硅氢化反应“和“催化不对称反应的发展”。本项目不仅利用典型元素的特征创造各种新的不对称反应，而且将许多对映体和非对映体选择性反应应用于复杂的多手性化合物包括有用的天然产物的合成。在1993-1995年期间，许多新的不对称或立体选择性反应都与Diels-Alder反应有关（山本），质子化（Yamamoto），双烯酮与醛的加成开环反应（Oguni），羟醛缩合反应（Shioiri），甲硅烷基乙炔与羰基化合物的加成（Shioiri），炔基的1，2-重排（Suzuki），金属-烯反应（Suzuki），分子内硅氢化（Tamao），开发了醛与二乙基锌的加成（Nakai）和烯丙基化（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.