0000000000431361
AUTHOR
Salah‐e. Stiriba
Chiral Organometallic Triangles with Rh−Rh Bonds. 2. Compounds Prepared from Enantiopure cis-Rh2(C6H4PPh2)2(OAc)2(HOAc)2 and Their Catalytic Potentials
Enantiomers of the orthometalated dirhodium compound cis-Rh2(C6H4PPh2)2(OAc)2(HOAc)2 (R-1 and S-1) were prepared from carboxylate exchange reactions of the resolved diasteroisomers of cis-Rh2(C6H4PPh2)2(protos)2(H2O)2 (protos = N-4-methylphenylsulfonyl-l-proline anion) and acetic acid. These compounds react with excess Me3OBF4 in CH3CN, producing the enantiomers of [cis-Rh2(C6H4PPh2)2(CH3CN)6](BF4)2 (R-2 and S-2) which have six labile and replaceable CH3CN ligands in equatorial and axial positions. Reactions of R-2 and S-2 with tetraethylammonium salts of the linear dicarboxylic acids, terephthalic acid (HO2CC6H4CO2H), oxalic acid (HO2CCO2H), and 4,4'-diphenyl-dicarboxylic acid (HO2CC6H4C6H…
Novel unsymmetrical ortho-metalated dirhodium (II) catalysts: trans influence of the axial ligand
Inductive effects of an X axial group which are transmitted through the RhRh bond influence the reactivity of ortho-metalated dirhodium complexes 3 in the cyclization of 1-diazo-5-penten-2-one (4).
Synthesis of Natural Products By Rhodium-Mediated Intramolecular C-H Insertion
The strategic advantages of the Rh-mediated intramolecular C–H insertion, which has been used as the key step in several natural product syntheses, are described here. The most recent such synthesis is the elegant route to (+)-morphine shown below.
ChemInform Abstract: Novel Unsymmetrical ortho-Metalated Dirhodium(II) Catalysts: trans Influence of the Axial Ligand.
Inductive effects of an X axial group which are transmitted through the RhRh bond influence the reactivity of ortho-metalated dirhodium complexes 3 in the cyclization of 1-diazo-5-penten-2-one (4).