Design of Fine Acid Base Catalysts and their Utility in Selective Organic Synthesis

精细酸碱催化剂的设计及其在选择性有机合成中的应用

基本信息

批准号：
13853003
负责人：
MARUOKA Keiji
金额：
$ 79.29万
依托单位：
KYOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (S)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2005
项目状态：
已结题

项目摘要

In this research project, we focused our attention on the rational design of truly efficient acid/base catalysts for the development of synthetic processes in order to achieve the high reactivity and selectivity, not observable by ordinary, acid/base catalysts. In the sophisticated Lewis acid chemistry, a new, chiral bidentate Ti(IV) complex was successfully designed and can be utilized for simultaneous coordination to aldehyde carbonyls, thereby allowing the precise enantioface discrimination of such carbonyls for a new catalytic, practical enantioselective allylation of aldehydes with allyltributyltin. This chiral bidentate Ti(IV) complex has been successfully applied to asymmetric 1, 3-dipolar cycloaddition of nitrones or diazoacetates. On the other hand, phase transfer catalysis is a very useful approach that typically involves simple experimental operations, mild reaction conditions, inexpensive and environmentally benign reagents and solvents, and the large-scale reactions. Accordingly, structurally rigid, chiral spiro ammoniurn salts derived from commercially available (S)- or (R)-binaphthol have been designed as new C_2-symmetric chiral phase transfer catalysts and successfully applied to the highly efficient, catalytic enantioselective synthesis under mild phase transfer conditions. Quite recently, we have successfully designed simplified, yet very active chiral phase transfer catalysts for practical asymmetric synthesis of α-alkyl- and α,α-dialkylamino acids. In addition, chiral, helical-type phase transfer catalysts were newly designed for effecting asymmetric Strecker reaction for large-scale production of sterically hindered α-alkylamino acids. A bowl-shaped organometallic host, tris(2, 6-diphenylbenzyl)-silyl, -germyl, and -tin compounds can be prepared, and applied to selective organic transformations.

在该研究项目中，我们专注于真正有效的酸/碱催化剂的合理设计，以开发合成过程，以达到高反应性和选择性，而不是普通的酸/碱催化剂可观察到的。在复杂的刘易斯酸化学中，成功设计了一种新型的手性边界Ti（IV）复合物，并可以同时协调以醛的醛来进行协调，从而可以精确地对这种羰基抗性，以与新的含有型含有的carbonyls抗体，将其与实用的同型化合物替代化。这种手性边界Ti（IV）复合物已成功地应用于硝基或重生乙酸盐的不对称1，3-二极性环节。另一方面，相位转移催化剂是一种非常有用的方法，通常涉及简单的实验操作，轻度反应条件，廉价且环保的良性试剂和溶液以及大规模反应。根据相关的，在结构刚性的，手性的螺旋氨基销售中，从市售（S） - 或（R） - 双苯二酚被设计为新的C_2-对称性手性相位转移催化剂，并成功地应用于轻度，催化的，催化的对元素式合成的合成条件下。最近，我们成功地设计了简单但非常活跃的手性相转移催化剂，用于对α-烷基和α，α-二烷基氨基酸的实际不对称合成。此外，新设计的手性，螺旋型相转移催化剂是针对不对称的Strecker反应的，用于大规模生产在空间障碍的α-烷基氨基氨基中。可以制备碗形有机宿主Tris（2，6-二苯基苯基苯基）-silyl，-mermyl和-tin化合物，并应用于选择性有机转化。