A catalytic asymmetric Henry reaction has been developed with use of a sulfonyldiamine-CuCl complex as a catalyst. A series of new binaphthyl-containing sulfonyldiamine ligands (2a-h) were readily synthesized in two steps starting from commercially available chiral 1,2-diamines. The (R,R)-diamine-(R)-binaphthyl ligand (2d)-CuCl complex smoothly catalyzed the enantioselective Henry reaction with the assistance of pyridine to give the corresponding adduct with high enantiomeric excess (up to 93%). Moreover, the 2d-CuCl-pyridine system promotes the diastereoselective Henry reaction in syn-selective manner to give the adduct in up to 99% yield with 92:8 syn/ anti selectivity. The enantiomeric excess of the syn-adduct was 84% ee.

The first catalytic asymmetric [3 + 2] cycloadditions of Schiff bases of alpha-aminophosphonates with olefins have been developed. Chiral silver amide complexes bearing (R)-DTBM-SEGPHOS worked well as catalysts for the first time, and proline phosphonic analogues were obtained in high yields with excellent exo- and enantioselectivities.

Nitro alcohols P 0125 Asymmetric syn-Selective Henry Reaction Catalyzed by the Sulfonyldiamine-CuCl-Pyridine System. -(ARAI*, T.; TAKASHITA, R.; ENDO, Y.; WATANABE, M.; YANAGISAWA, A.; J. Org. Chem. 73 (2008) 13, 4903-4906; Dep. Chem., Fac. Sci., Chiba Univ., Inage, Chiba 263, Japan; Eng.) -Jannicke 48-048

Chiral Silver Amide Catalyzed Enantioselective [3 + 2] Cycloaddition of α-Aminophosphonates with Olefins. -Excellent exo-and enantioselectivities are observed. -(YAMASHITA, Y.; GUO, X.-X.; TAKASHITA, R.; KOBAYASHI*, S.;