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

本项目将把本实验室开发的新型手性伯胺-硫脲和胍-硫脲催化剂的应用范围扩展到以N-叔丁氧羰基亚胺为底物的其他有用反应（如Strecker合成、Mannich和aza-Henry反应等），以及通过Diels-桤木和杂-Diels-桤木反应合成天然产物。进一步设计和合成新的双功能框架，其包含路易斯碱单元（e. G.甲酰胺、亚砜等）和硫脲部分，并且可以通过非共价相互作用同时活化亲核试剂和亲电试剂。进一步的目标是开发适用于合成吡唑烷（一类有趣的杂环化合物）的不对称有机催化形式的[3+2]环加成反应，以及开发在水存在下用于不同有机转化而不使用有机溶剂的新有机催化体系。这项研究的特点是密切合作和不断反馈之间的理论研究，利用电子结构计算和统计速率理论和实验。

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.