Homogeneously catalyzed cleavage of C-O bonds and related reactions

该项目的目标是进一步开发均相钯催化的C-O键氢解反应。它包括机理研究、催化剂构效关系研究和动力学研究，以寻找更具活性和选择性的催化剂，并深入了解反应机理。计划进行系统的底物范围筛选，包括对各种官能团和结构特征的评估。在生物活性化合物的合成和天然化合物的后期功能化过程中，将展示这种转化的合成效用。应使用相应的手性催化剂来开发立体选择性变体。这将包括叔醇的动力学拆分、去对称化和对映选择性氢解。此外，还应研究与之相关的还原半片呐醇重排反应。

The aim of the project is further development of homogeneous palladium-catalysed hydrogen-lysis of C-O bonds. It includes a mechanistic catalyst structure-activity relationship study and kinetic investigation in order to identify a more active and selective catalyst and to gain insight into the reaction mechanism. A systematic substrate scope screening is planned, including evaluation of various functional groups and structural features. The synthetic utility of the transformation will be demonstrated in synthesis of biologically active compounds, as well as in the late stage functionalization of natural compounds. A stereoselective variation should be developed employing a corresponding chiral catalyst. This will include kinetic resolution, desymmetrization and enantioselective hydrogenolysis of tertiary alcohols. Furthermore, the related reductive semipinacol rearrangement should be investigated.