Synthesis Of Chiral Br(?)nsted Acid Catalysts And Their Application For Asymmetric Reactions

Organocatalysts have been widely applied in asymmetric synthesis, especially in enantioselective C-C bond forming reactions, such as Mannich-Type reaction. Friedel-Crafts reaction. Morita-Baylis-Hillman (MBH) reaction and so on.In this paper, firstly, (R)-(-)-1,1'-Binaphthalene-2,2'-sulfonimide(M-4) was synthesized from (R)-Binaphthol through reactions of acylation,Newman-Kwart rearrangement, oxidation reaction and Cyclization. based on the structure of catalyst M-4. the compounds M-6 and M-7 were obtained through reactions of Halogenated reaction and Alkylation. The catalysts M-4 M-6 M-7 were then applied in the Mannich-Type reaction and in the Friedel-Crafts reaction, separately. Under the optimized conditions, catalyst M-4 exhibited good catalytic activity, Friedel-Crafts products were obtained with moderate enantioselectivity (20%).Secondly, (R)-VAPOL and (S)-VAPOL were synthesized from the 2-naphthylacetic acid through reactions of couple reaction and chiral resolution. And then (R)-Binaphthol and (R)-VAPOL were applied in MBH reaction of aldehyde and acrylate. Under the optimized conditions (at 25℃.using CH2Cl2 as the solvent). (R)-VAPOL exhibited high catalytic activity, MBH adducts were obtained with high enantioselectivity (96%).This study just provided preliminary results of our work on the development of new chiral Brφnsted acid catalysts. Further studied on the substrate scope and the synthetic applications of these catalysts are currently underway.