Structural and configurational metal complex-substrate-product relationships in asymmetric catalytic hydrogenation, hydrosilylation and cross-coupling reactions

Today's data about the relationship between the structures of catalytic rhodium, iridium, ruthenium, nickel and cobalt complexes and the substrate in homogeneous asymmetric hydrogenation, hydrosilylation and cross-coupling are described systematically. On the basis of the criterion of maximum enantioselectivity of the catalytic complex, the optimal ratio of the number of coordination vacancies of the complex and the number of functional groups of the substrate is estimated. The relationship between the configurations of the complex and the product in the title reactions is analyzed. It is shown that the use of C2-symmetric chiral diphosphine complexes whose ligands have a constituent shaped like an incomplete convolution of a helix around the central metal atom results in the formation of products with a strictly definite configuration typical of the given sign of the helix from one-type substrates