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Chiral N-Heterocyclic Carbenes with Restricted Flexibility in Asymmetric Catalysis

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posted on 2007-01-29, 00:00 authored by Denys Baskakov, Wolfgang A. Herrmann, Eberhardt Herdtweck, Stephan D. Hoffmann
A chiral C2-symmetric diamine was prepared from (S)-3-phenyl-3,4-dihydroisoquinoline by the virtue of asymmetric transformation. Rhodium and iridium complexes of chiral N-heterocyclic carbenes with restricted flexibility derived from 3,3‘-substituted partially reduced biisoquinoline were obtained by transmetalation from the corresponding silver(I) complexes. Unexpected double-bond formation in the carbene ligand has occurred during a transmetalation step. The structures of these complexes were verified by X-ray diffraction. Metal complexes of these N-heterocyclic carbenes were applied to the asymmetric hydrogenation of methyl 2-acetamidoacrylate. Good enantioselectivities of up to 67% ee were achieved.