Copper-Catalyzed Regio- and Stereoselective Aminochlorinations

Abstract

A new method of obtaining vicinal haloamino nitriles is described using convenient catalytic conditions. Using CuI and molecular sieves, good yields and good regio- and stereo­selectivities are seen for aminochlorinations of tri- and tetrasubstituted cyano olefins. A moderate scope is shown with electron-withdrawing, electron-donating, and electron-neutral groups on the olefin to provide vicinal haloamino nitriles in good yields and stereoselectivities. Interestingly, opposite regiochemistries were seen for the α-substituted cinnamonitrile substrates compared to the β-substituted ones. For the latter substrates, the products of their aminochlorinations can be easily converted into desirable β-amino acids.