Ruthium-Catalyzed Olefin Metathesis Reactions And Organocatalytic Alkylations

Ruthium-catalyzed olefin metathesis and organocatalysis are the most attractive area in organic chemistry. This thesis is focusing on the synthesis of new chemicals which have potential utilities as pestcides and hybrid material with the use of olefin metathesis and organocatalysis as well as the combination of these powerful strategies.(1) Olefin cross metathesis (CM) reaction of two electron-deficient olefin components is very rare in the literature. With the use of new-developed Ru carbene catalysts, we have carried out the CM reaction ofα,β-unsaturated phosphonates with crotonaldehyde derivatives.(2) We have successfully established a novel enantioselective synthesis ofα-indolyl phosphonates via organocatalytic Friedel-Crafts alkylation of substitued indoles with (E)-dialkyl 3-oxoprop-1-enylphosphonates. The reaction exhibits great enantioselectivity (up to 96% ee). (3) The preparation of fine chemicals from natural, renewable, organic raw materials is an attractive topic of research, especially when its aim is the recycling of agro-industrial by-products through environmentally sustainable processes. We have studied on the synthesis of new meso-tetraarylporphyrins, fulleropyrrolidines bearing cardanol, and further transformation of the unsaturated chains, especially using olefin metathesis protocols. Due to the presence of the long alkyl side-chain on the aryl ring, the meso-tetraarylporphyrins and cardanol fulleropyrrolidine hybrids exhibit solubility in organic solvents 100-300 times higher than that of unsubstituted porphyrins and fulleropyrrolidines.(4) Combining Ru-catalyzed olefin metathesis with organocatalytic alkylation, we have carried out the asymmetric synthesis of benzene-fused oxygen heterocycles with various ring size. It is worthy to note that the benzene-fused eight-membered oxygen heterocycles could exhibite excellent allelopathic activities and pesticide activities.