Copper-catalyzed nitrogen transfer reactions

Abstract

Part 1. Cu-Catalyzed Aziridination with Chelating 2-Pyridiyl Nitrogen Sources

We have developed, on the basis of a chelation-strategy, an efficient copper-catalyzed aziridination protocol with the use of 5-methyl-2-pyridinesulfon amide and $PhI(OAc)_2$ or 2-pyridinesulfonazide. The reaction proceeds smoothly under mild conditions to give aziridines in moderate to good yields in the absence of external ligands or bases. The coordination-assisted approach offers the additional benefits that efficient deprotection of the N-substituent and selective aziridine ring-opening are effectively achieved. Further, detail mechanism of aziridination was investigated by X-ray crystallography, ESI-MS, UV, Hammett plot, kinetic study, computational calculations. We got to bottom of more advanced aziridination with chelation-assisted strategy by mechanism sutides. Additionally, metal-free decarbonylative aziridnation applicated chelation-approach was exploited successfully.

Part 2. Cu-Catalyzed Three-Component Synthesis of N-Sulfonylamidines with Sulfonazides, Alkynes, and Amines

We have developed a highly efficient, mild, practical, and catalytic method for the synthesis of N-sulfonylamidines. This MCR has an extremely broad scope with all three coupling components of alkyne, sulfonylazide, and amine.