Amines bearing tertiary substituents by tandem enantioselective carbolithiation-rearrangement of vinylureas.

Michael Tait, Morgan Donnard, Alberto Minassi, Julien Lefranc, Beatrice Bechi, Giorgio Carbone, Peter O'Brien, Jonathan Clayden

School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK.

Organic letters 2013 Jan 4

filter terms:

In the presence of (-)-sparteine or a (+)-sparteine surrogate, organolithiums add to N-alkenyl-N'-arylureas to give benzylic organolithiums in an enantioselective manner. Under the influence of DMPU, these organolithiums undergo rearrangement with migration of the N'-aryl ring from N to C, leading to the urea derivatives of enantiomerically enriched amines bearing tertiary substituents. Basic hydrolysis returns the functionalized amine, providing a new synthetic route to compounds with quaternary stereogenic centers bearing nitrogen.

Citation

Michael Tait, Morgan Donnard, Alberto Minassi, Julien Lefranc, Beatrice Bechi, Giorgio Carbone, Peter O'Brien, Jonathan Clayden. Amines bearing tertiary substituents by tandem enantioselective carbolithiation-rearrangement of vinylureas. Organic letters. 2013 Jan 4;15(1):34-7