Synfacts 2007(7): 0734-0734  
DOI: 10.1055/s-2007-968620
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York

syn-Selective Catalytic Asymmetric Nitro-Mannich Reactions

Contributor(s): Mark Lautens, Praew Thansandote
S. Handa, V. Gnanadesikan, S. Matsunaga*, M. Shibasaki*
The University of Tokyo, Japan
Further Information

Publication History

Publication Date:
22 June 2007 (online)

Significance

This communication highlights the first syn-selective catalytic asymmetric nitro-Mannich reaction. The catalyst consists of a hetero­bimetallic Cu-Sm-Schiff base complex synthesized from a dinucleating Schiff base ligand in two steps. The scope is broad with a variety of N-Boc imines affording high yields, syn selectivities, and enantioselectivities, including imines with electron-donating, electron-withdrawing, and hetero­aryl substituents. Even isomerizable alkyl N-Boc imines and use of nitropropane instead of nitro­ethane afford high yields and selectivities. The synthetic utility is demonstrated by converting one of the products into syn-1,2-diamines in two steps and with excellent yields.