Synfacts 2011(8): 0861-0861  
DOI: 10.1055/s-0030-1260749
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart ˙ New York

Stereodivergent Asymmetric Reactions of α-Isothiocyanato Ester with Ketimines

Contributor(s): Hisashi Yamamoto, Dmitry L. Usanov
G. Lu, T. Yoshino, H. Morimoto, S. Matsunaga*, M. Shibasaki*
The University of Tokyo and Institute of Microbial Chemistry, Tokyo, Japan
Further Information

Publication History

Publication Date:
20 July 2011 (online)

Significance

Until the disclosure of this work, there have been no reports on the catalytic asymmetric preparation of β-tetrasubstituted α,β-diamino acids or their surrogates, which represent an interesting structural motif in light of biological activity. The methodology reported herein employs the Mannich-type reaction of ketimines with α-methyl-α-isothiocyanato ester 1 mediated by Mg and Sr complexes of 2, which are notable for inducing the opposite enantiofacial selectivities leading to syn- and anti-diastereomers, respectively. Desulfurization as well as a Dpp removal-desulfurative coupling sequence were carried out on certain products demonstrating their synthetic utility.