碳碳三键选择性活化导向炔卤高效转化反应及机理研究

Selective carbon carbon triple bonds activation is the key step in alkynes transformations, and is also a basic method for efficient utilization of alkynes. The development of simple and efficient carbon carbon triple bonds activation strategy is an important but also challenging research project in organic chemistry. Haloalkynes are readily available synthons, in which the carbon carbon triple bonds directly connect to halogen atoms. This project bases on the important topic of efficient transformation and application of haloalkynes, focuses on the limitation of haloalkynes carbon carbon triple bonds conversion diversity, proposes to develop new strategies for the highly efficient and selective activation of the haloalkynes carbon carbon triple bonds, realizes the efficient conversion of the carbon carbon triple bonds of haloalkynes to carbon carbon double bonds, carbon carbon single bonds and also the complete cleavage of haloalkynes carbon carbon triple bonds, explores the key factors that contributes the efficient activation of haloalkynes carbon carbon triple bonds and controls the selectivity of bonds cleavage and formation, and finally clarifies the reaction mechanism. On the basis of these studies, we will solve the challenge of bonds cleavage and formation involved in the process of haloalkynes carbon carbon triple bonds transformation, developing new methods for bonds cleavage and construction, also solve the regio- and diastereoselectivity problems involved in the transformation of haloalkynes carbon carbon triple bonds. We will develop new catalytic systems for the activation of haloalkynes carbon carbon triple bonds, providing new methods for the efficient utilization haloalkynes and complex molecules synthesis.

碳-碳三键的选择性活化是炔烃参与反应的关键步骤，是炔烃高效利用的基本手段。如何发展简单高效碳-碳三键活化策略一直是有机化学的重要问题，也是具有挑战性的研究课题。炔卤是一类碳-碳三键与卤素原子直接相连的有机化合物，是一种廉价易得的合成砌块。本项目基于炔卤化合物的高效转化与应用这个重要课题，针对炔卤碳-碳三键转化多样性不足的问题，拟发展炔卤碳-碳三键高效、高选择性活化新策略，实现炔卤碳-碳三键到碳-碳双键或碳-碳单键以及炔卤碳-碳三键完全切断的高效转化新反应，探索反应过程中高效活化炔卤碳-碳三键和调控其选择性断键与成键的关键因素，弄清反应机理。通过这些反应研究，我们将解决炔卤碳-碳三键高效转化过程中的断键与成键问题，发展新的断键与成键方法；解决炔卤碳-碳三键高效转化过程中所涉及区域选择性和非对映选择性问题；发展炔卤碳-碳三键高效活化新催化体系，为炔卤的高效利用及复杂分子的合成提供新方法。

功能分子化合物的绿色精准创制与应用是有机合成化学的研究前沿及难点课题之一。本项目针对炔卤化合物转化反应过程中存在的问题，开展了炔卤参与的碳-碳三键转化反应研究，包括碳-碳三键转化为碳-碳双键，碳-碳三键转化为碳-碳单键等，发展了炔卤化合物碳-碳三键可控性转化新方法、新反应，高选择性构建了多种功能的N1-（2,2,2-三氟-1-芳基乙基）-三氮唑衍生物、稠环环丙烷化合物、三氟甲基炔硫醚化合物等。在研究炔卤碳-碳三键可控性转化反应的过程中，我们还发现了一些新的转化反应，构建了多种含氟及杂环化合物；利用各种仪器方法对反应机理进行了研究，捕捉并表征了反应关键中间体，提出并验证了反应机理；并将所发展方法应用于一些功能活性分子的合成。本项目的完成在理论上丰富了炔卤、含氟烯烃等简单易得砌块化学转化的理论内涵，在应用方面，为一些功能分子的合成提供了简单高效途径。