RESUMO
A series of redox-responsive ferrocenyl-substituted boranes and boronic esters were synthesized. Oxidation of the ferrocenyl ligand to the ferrocenium resulted in a drastic increase in the Lewis acidity beyond the strength of SbF5 , which was investigated experimentally and computationally. The resulting highly Lewis acidic boron compounds were used for catalytic C-F and S-F bond activation.
RESUMO
The metal-free catalytic hydrogenation of secondary carboxylic acid amides is developed. The reduction is realized by two new catalytic reactions. First, the amide is converted into the imidoyl chloride by triphosgene (CO(OCCl3 )2 ) using novel phosphorus(V) catalysts. Second, the inâ situ generated imidoyl chlorides are hydrogenated in high yields by an FLP-catalyst. Mechanistic and quantum mechanical calculations support an autoinduced catalytic cycle for the hydrogenation with chloride acting as unusual Lewis base for FLP-mediated H2 -activation.
RESUMO
The potential of two chiral amidines and three non-chiral boranes in the metal-free hydrogen activation was explored. The resulting chiral amidiunium borohydride salts were investigated in asymmetric hydrogenation reactions of ketimines, activated double bonds and dehydro amioacid esters.