Conjugate Addition And Allylation Reaction Catalyzed By Sulfido-Bridged Multimetal Clusters With Cp~* Ligands

Metal-sulfur clusters have significant biologic and physiological activity and are found in nature. Generally, researches about metal-sulfur clusters are focused on the functional simulation of enzyme, whiles the reports on their catalytic activity are few. In this thesis, we investigate the catalytic activity of the thiolate-bridged diruthenium complexes and cubane-type clusters for conjugate addition and allylation reaction, respectively. The detailed contents are as follows:(1) The facilely and efficient conjugate addition reaction of electron-deficient olefins with nucleophiles catalyzed by thiolate-bridged diruthenium complex [Cp*Ru(μ2-SEt)3RuCp*] (Cp*=η5-C5Me5) under mild conditions has been developed. A variety of olefins and N,O, S nucleophiles are investigated, and under 1 mol% catalyst loading with solvent, or lower catalyst loading 0.1 mol% without solvent, the results are both satifying, and we get anti-Markovnikov products with high yield.(2) A highly efficient and regioslective allylation reaction of amines with allylic alcohols catalyzed by the cubane-type sulfide cluster [(Cp*Mo)3S4Pd(dba)] [PF6] has been developed with H3BO3 as an additive under mild conditions. A variety of amines and allylic alcohols are investigated, and in the case of allylic alcohols bearing substituents at either a- or y- position only linear allylic amination products are obtained.(3) The novel [Mo3S4Pd(η3-allyl)] clusters are synthesized by treating [(Cp*Mo)3S4Pd (dba)][PF6] with corresponding allylic halides and AgPF6. Their structures are confirmed by X-ray diffraction analysis and NMR characterization. A highly efficient and regioselective allylation reaction of amines and active methylene compounds directly using allylic alcohols under mild conditions has been developed by using [Mo3S4Pd(η3-allyl)] clusters as catalyst. A variety of allylic alcohols and nucleophiles are investigated, and in the case of allylic alcohols bearing substituents at either a- or y- position only linear allylic amination products are obtained.(4) The Friedel-Crafts alkylation reaction of allylic alcohols with electron-rich arenes and indole compounds catalyzed by [Mo3S4Pd(η3-allyl)] clusters is studied. With 3 mol% catalyst loading, the alkylation products of p-position to amino in arenes and C3 position in indole compounds are obtained, respectively.