Enantioselective synthesis of protected amines via the catalytic asymmetric addition of hydrazoic acid to ketenes

ORGN 382

Xing Dai, xingdai@mit.edu1, Takashi Nakai1, Jan A. C. Romero1, and Gregory C. Fu2. (1) Department of Chemistry, Massachusetts Institute of Technology, Room 18-343, 77 Massachusetts Avenue, Cambridge, MA 02139, (2) Department of Chemistry, MIT, 77 Mass. Ave., Room 18-290, Cambridge, MA 02139
The first effective method for the conversion of achiral ketenes into enantioenriched protected amines has been developed. In the presence of a new planar-chiral DMAP catalyst, hydrazoic acid was added to ketenes, followed by Curtius rearrangement, generating chiral primary amine derivatives in good yield and ee. Mechanism studies suggested this reaction is a Brønsted acid catalyzed process. The scope of this chemistry will be discussed.

 

Asymmetric Reactions and Syntheses
8:00 AM-12:00 PM, Tuesday, August 21, 2007 BCEC -- 253C, Oral

Division of Organic Chemistry

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