| Abstract: | Asymmetric catalysis of metal carbene transformations with unique chiral dirhodium(II) carboxamides provides highly enantioselective and diastereoselective synthesesvia cyclopropanation, cyclopropenation, and carbon-hydrogen insertion reactions of diazoesters and diazoamides. Constructed from a dirhodium(II) core with bridging pyrrolidone, oxazolidinone, or imidazolidinone ligands, these catalysts are especially effective for intramolecular transformations that occur in high yield with greater than 90 % enantiomeric excess (ee) and high diastereocontrol.Based on lectures given at the 1994 International INEOS Workshop, May 21–26, 1994, and at the Nesmeyanov Institute of Organoelement Compounds, Moscow, on May 30, 1994.On the occasion of the award of a D. Sc. (honoris causa) degree to Prof. M. P. Doyle for his works on catalytic enantioselective syntheses by the Russian Academy of Sciences in 1994.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1879–1892, November, 1994. |
