Asymmetric Synthesis Of CF₂-aziridines Under The Catalysis Of Chiral BINOL-derived Disulfonimide And Arylboronic Acid

Fluorinated aziridine is a type of molecular building block with important synthetic value and medicinal potential,but the synthesis of chiral aziridine compounds with fluorine-containing functional groups is rare.In particular,available asymmetric catalytic method to access chiral difluoro-functionalized aziridines is still lacking,thus leaving significant research space for new reaction development.This thesis describes an asymmetric aziridination reaction of benzenesulfonyl difluorodiazoethane(Ph SO₂CF₂CHN₂)with aldimine formed in-situ from arylglyoxal monohydrate and 4-methoxyaniline,providing a stereoselective synthetic method for chiral difluoro-containing functionalized aziridines.The key to realizing this multi-component reaction is to use a combined strong Br(?)nsted acid composed of disulfonimide derived from chiral binaphthol and o-carboxyphenylboronic acid as a synergistic catalytic system.The ee value of the obtained aziridine product is 35–73%.Through a practical dissolution-filtration procedure(the corresponding aziridine product was dissolved in an appropriate amount of isopropanol under ultrasound,and then the mother liquor was collected by filtration.The remaining solids continued to be dissolved with an appropriate amount of isopropanol under ultrasound.The above operation was repeated until the ee value of the mother liquor was lower than 90%.),the optical purity of difluorosubstituted aziridine can be further improved to 95–>99%ee.