Thiamine-inspired novel organocatalytic reactions with heterazolium precatalysts

硫胺素启发的杂唑鎓预催化剂的新型有机催化反应

基本信息

批准号：
172089892
负责人：
Professorin Dr. Kirsten Zeitler
金额：
--
依托单位：
Institut für Organische Chemie
依托单位国家：
德国
项目类别：
Research Units
财政年份：
2010
资助国家：
德国
起止时间：
2009-12-31 至 2017-12-31
项目状态：
已结题

来源：
https://gepris.dfg.de/gepris/projekt/172089892?language=en
关键词：
Thiamine inspired novel organocatalytic reactions

项目摘要

With respect to the continuously increasing complexity of organic target molecules the ongoing development of new synthetic methods and improvement of known transformations can be seen as a perpetual goal of chemical research. In this context, organocatalytic processes are gaining importance in the field of asymmetric synthesis; in particular as these methods otter both easy to- handle, metal-free reaction conditions and, moreover, new modes of actions for catalytic transformations, such as umpolung reactivity. Within the scope of this project the improvement of N-heterocyclic carbene (NHC)-catalyzed reactions will be attempted in a synergistic, multidisciplinary approach. At the interface of enzyme and organic catalysis we aim to transfer insights from both fields in a bidirectional way to allow for improvement and development of new methods. With this prerequisite it is the objective of this project to mimic the activity of thiamine diphosphate (ThDP)-dependent enzymes. Specifically, we will investigate catalytic bondcleaving reactions for the synthesis of w-functionalized molecules based on their enzymatic archetypes and additionally, apply insights into the Stereodifferentiation within the enzymes active sites to improve stereoinduction in carbene catalysis. A further goal of this project is the application of synthetic based knowledge to enzyme catalysis, which will be realized in cooperative projects including the employment of alternative substrates and the implementation of novel coenzyme analogues for ThDP-dependent enzymes.

关于有机靶标分子的不断增长的复杂性，新合成方法的持续发展和改善已知转化可以看作是化学研究的永久目标。在这种情况下，有机催化过程在不对称合成领域变得重要。特别是由于这些方法既易于处理，无金属反应条件，又是催化转化的新作用，例如Umpolung反应性。在该项目的范围内，将尝试以协同的多学科方法来改善N-杂环卡宾（NHC）催化反应。在酶和有机催化的界面上，我们旨在以双向方式从两个领域转移见解，以改善和开发新方法。有了这个先决条件，该项目的目的是模仿硫胺素二磷酸（THDP）依赖性酶的活性。具体而言，我们将研究基于酶原型合成W-官能化分子的催化键切的反应，并在酶活性位点内对立体差异的洞察力进行洞察力，以改善在碳酸催化中的立体诱导。该项目的另一个目标是将基于合成的知识应用于酶催化，该知识将在合作项目中实现，包括使用替代底物以及实施新颖的辅酶类似物的THDP依赖性酶。