Application Of Novel Chiral Sulfoxide Ligands In Asymmetric Catalysis

In recent years, the asymmetric synthesis has been paid more and more attention and it has become the hot spot and front edge of the organic chemistry, which also represents the developmental direction of organic synthetic chemistry in the 21st century. The asymmetric catalytic reaction is the most effective one in the asymmetric synthesis, which has the most economic value. Consequently, designing and synthesis of chiral ligands provide the easy and efficient way for asymmetric catalysis. Study on the catalytic asymmetric synthesis has made a big breakthrough for decades and in recent years stereoselective synthesis of biologically active heterocyclic skeletons by chiral ligands have made considerable progress.The main work of this thesis is based on two types of chiral sulfoxide ligands. These two ligands were applied to the asymmetric Henry reaction/iodocyclization of γ,δ-unsaturated aldehydes for construction of chiral tetrahydrofuran derivatives and the asymmetric allylic alkylation reaction of indoles. The details are as follows:First of all, we made a further structure optimization of the novel sulfoxide alkali chiral ligands. Then we applied these ligands to the asymmetric Henry reaction of γ,δ-unsaturated aldehydes. We also carried out a one-pot of the asymmetric Henry reaction and iodocyclization strategy to synthesize a series of 2,2,5-trisubstituted tetrahydrofuran skeletons with high yields (up to 99% yield) and high enantioselectivities (up to 97% ee). At the same time, we also transfered the nitro group to amino group.The strategy didn’t affect the enantioselectivities while the diastereoselectivities were also obtained with good control.In addition, in order to further verify the superiority of sulfoxide ligands, we applied another type of sulfoxide phosphine ligand to asymmetric allylic alkylation reactions of indole. By this reaction, a variety of asymmetric N-functionalized indoles were achieved (up to 98% yield,98% ee). The method can also be used for asymmetric allylic alkylation reaction of other N-containing heterocycles such as benzotriazoles, imidazoles, pyrroles, benzimidazoles and so on.