Origin of enantioselectivity in the asymmetric Ru-catalyzed metathesis of olefins.
The mechanism of enantioselectivity in the asymmetric Ru-catalyzed metathesis of olefins is investigated with a theoretical approach. The models are based on the chiral N-heterocyclic (NHC)-based catalysts developed by Grubbs. Our analysis indicates that the origin of enantioselectivity in the ring-closing metathesis of achiral trienes is correlated to the chiral folding of the N-bonded aromatic groups, which is imposed by the Ph groups in positions 4 and 5 of the imidazole ring of the NHC ligand. This chiral folding of the catalyst imposes a chiral orientation around the Ru=C bond, which, in turn, selects between the two enantiofaces of the substrate. In the ring-closing transition state, the geometry in which additional groups on the forming ring are in pseudoequatorial positions is favored over transition states in which this additional group is in a pseudoaxial position. These combined effects rationalize the enantiomeric excesses experimentally obtained.
Dipartimento di Chimica, Università di Salerno, Via Salvador Allende, Baronissi (SA) I-80184, Italy.
Chiara
C
Costabile
Luigi
L
Cavallo