Chiral porphyrin complexes of cobalt(II) and ruthenium(II) in catalytic cyclopropanation and amination reactions

The authors report here the syntheses of two new metal complexes (M= Co, 2; M= Ru(CO), 3) of the chiral porphyrin TmyrtP (1, TmyrtP= dianion of the meso-tetrakis[(1R)-apopinen-2-yl]porphyrin). Both complexes exist as a mixt. of atropisomers. Complexes 2 and 3 activate arom. azides for the amination under mild conditions of unsatd. hydrocarbons. Even though the obsd. ee values are low, this is the 1st asym. transfer of the nitrene residue of aryl azides to a prochiral olefin catalyzed by a transition metal complex to be reported in the literature. Complex 3 also showed a good catalytic activity in cyclopropanation reactions with ethyldiazoacetate even at low temps. (-30 Deg) but a poor diastereo- and enantioselectivity were obsd.