Chiral mono- and bifunctional organic catalysts: A joint experimental-theoretical approach to asymmetric organic synthesis

手性单功能和双功能有机催化剂：不对称有机合成的联合实验理论方法

• 批准号: 5451529
• 负责人: Professor Dr. Timothy Clark
• 金额: --
• 依托单位: Computer-Chemie-Centrum (CCC)
• 依托单位国家: 德国
• 项目类别: Priority Programmes
• 财政年份: 2005
• 资助国家: 德国
• 起止时间: 2004-12-31 至 2011-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/5451529?language=en
• 关键词: Chiral; mono; bifunctional; organic; catalysts

In this project the scope of the new chiral primary amine-thiourea and guanidine-thiourea catalysts developed in our laboratory will be extended to other useful reactions that can use N-Boc-imines as substrates (e.g. the Strecker synthesis, Mannich and aza-Henry reactions, etc.), and to natural product syntheses via Diels-Alder and hetero-Diels-Alder reactions. Further design and synthesis of new bifunctional frameworks that contain both the Lewis-base unit (e. g. formamides, sulfoxides, etc.) and the thiourea moiety, and that can activate both nucleophiles and electrophiles simultaneously via non-covalent interactions, will be carried out. The development of an asymmetric organocatalytic version of [3+2] cycloaddition reactions that is applicable to the synthesis of pyrazolidines (an interesting class of heterocyclic compounds), and the development of new organocatalytic systems for different organic transformations in the presence of water without using organic solvents is a further goal. This research is characterized by close cooperation and continuous feedback between theoretical investigations that make use of electronic structure calculations and statistical rate theory and experiment.

在本项目中，我们实验室开发的新型手性伯胺-硫脲和胍-硫脲催化剂的范围将扩展到其他以n - boc -亚胺为底物的有用反应（如Strecker合成、Mannich和za- henry反应等），以及通过Diels-Alder和杂Diels-Alder反应合成天然产物。将进一步设计和合成新的双功能框架，这些框架既包含路易斯碱基单元（如甲酰胺、亚砜等），也包含硫脲部分，并且可以通过非共价相互作用同时激活亲核试剂和亲电试剂。进一步的目标是开发一种适用于合成吡唑烷（一类有趣的杂环化合物）的[3+2]环加成反应的不对称有机催化版本，以及在不使用有机溶剂的情况下为不同的有机转化开发新的有机催化系统。本研究的特点是利用电子结构计算和统计速率理论与实验的理论研究之间的密切合作和持续反馈。