Nickel-catalyzed synthesis of acrylamides from alpha olefins and isocyanates

ORGN 27

Kristin D. Schleicher, schleich@mit.edu and Timothy F. Jamison. Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA 02139
The nickel(0)-catalyzed coupling of α-olefins and isocyanates proceeds in the presence of the N-heterocyclic carbene (NHC) ligand IPr to provide α,β-unsaturated amides. Carbon-carbon bond formation occurs preferentially at the 2-position of the olefin. This regioselectivity stands in contrast to a previously reported reaction that uses phosphines and favors coupling at the alkene 1-position. Bulky, electron-rich alkyl isocyanates are the best substrates for the nickel(0)-IPr catalyst system. The N-tert-butyl amide products can be converted to the corresponding primary amides under acidic conditions.

 

Metal-Mediated Reactions and Syntheses
8:00 AM-12:00 PM, Sunday, August 19, 2007 BCEC -- 254 A/B, Oral

Division of Organic Chemistry

The 234th ACS National Meeting, Boston, MA, August 19-23, 2007