Diastereaoselective transition Metal-catalysed azyridination of Olefins involving Chiral Iminoiodanes

ROBERT-PEILLAR F.; FRUIT, C; DI CHENNA PABLO H.; MULLER, P.; DODD, R. H.; DAUBAN, P.

Simposio; 18th French-Japanese Symposium on Medicinal and Fine Chemistry; 2005

  Transition metal-catalyzed aziridination of olefins is an efficient methodology for C-N bondformation that involves nitrene species generated from azides, chloramines or iminoiodanes.Among these nitrene precursors, the latter are of particular interest since their use in conjunctionwith copper catalysts has found applications in total synthesis.1 Moreover, enantioselectivenitrene transfer can be performed from iminoiodanes in the presence of chiral rhodium(II) orcopper(I) complexes.2The asymmetric copper- or rhodium-catalyzed aziridination of olefins suffers from its limitationto styrene type substrates. In order to broaden the scope of stereoselective C-N bond formation,we felt it interesting to generate chiral iminoiodanes in situ by applying one-pot methodologiespreviously developed in the laboratory3 or by the group of Du Bois,4 processes that greatlysimplify the troublesome handling of iminoiodanes and enhance the variety of nitrogenouscompounds able to be transferred. To this end, we turned our attention to sulfonimidamides,chiral sulfur(VI) reagents as potential chiral iminoiodane precursors. In this communication, thediastereoselective transition metal-catalyzed aziridination of olefins using these reagents will bepresented.1 Moreover, enantioselectivenitrene transfer can be performed from iminoiodanes in the presence of chiral rhodium(II) orcopper(I) complexes.2The asymmetric copper- or rhodium-catalyzed aziridination of olefins suffers from its limitationto styrene type substrates. In order to broaden the scope of stereoselective C-N bond formation,we felt it interesting to generate chiral iminoiodanes in situ by applying one-pot methodologiespreviously developed in the laboratory3 or by the group of Du Bois,4 processes that greatlysimplify the troublesome handling of iminoiodanes and enhance the variety of nitrogenouscompounds able to be transferred. To this end, we turned our attention to sulfonimidamides,chiral sulfur(VI) reagents as potential chiral iminoiodane precursors. In this communication, thediastereoselective transition metal-catalyzed aziridination of olefins using these reagents will bepresented.