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.

在这个研究项目中，我们将注意力集中在合理设计真正有效的酸/碱催化剂以开发合成工艺，以实现普通酸/碱催化剂无法观察到的高反应活性和选择性。在酸性化学中，成功设计了一种新型手性二齿 Ti(IV) 络合物，可用于与醛羰基同时配位，从而可以精确区分此类羰基，从而形成一种新的催化、实用的催化剂。这种手性二齿 Ti(IV) 络合物已成功应用于硝酮或重氮乙酸酯的不对称 1, 3-偶极环加成反应，而相转移催化是一种非常有用的方法，通常涉及简单的实验。操作，温和的反应条件，廉价且环境友好的试剂和溶剂，以及相应的结构上的大规模反应。由市售的(S)-或(R)-联萘酚衍生的刚性手性螺铵盐被设计为新型C_2对称手性相转移催化剂，并成功应用于温和相转移条件下的高效催化对映选择性合成。最近，我们成功设计了简化但非常活跃的手性相转移催化剂，用于α-烷基氨基酸和α,α-二烷基氨基酸的实际不对称合成。新设计了手性螺旋型相转移催化剂，用于大规模生产位阻α-烷基氨基酸的不对称Strecker反应。碗状有机金属主体，三(2, 6-二苯基苯甲基)-甲硅烷基，可以制备和-锡化合物，并应用于选择性有机转化。