0000000000539927
AUTHOR
† And Salah-eddine Stiriba
High Enantiocontrol in the Intramolecular Cyclopropanation of Diazo Ketones Catalyzed by Dirhodium(II) Complexes with Ortho-Metalated Aryl Phosphine Ligands
[reaction: see text]. Chiral dirhodium(II) complexes, Rh2(O2CCF3)2(PC)2, [PCH = (p-CH3C6H4)3P, (m-CH3C6H4)3P], provide an excellent yield and a high enantiocontrol in the cyclopropanation of alpha-diazo ketones with gamma and delta double bonds. The ee values are significantly dependent on the solvent used; the best results are obtained using pentane.
Ligand Effects on the Chemoselectivity of Ortho-Metalated Rhodium(II) Catalyzed α-Diazo Ketone Transformations
Rh2(OOCR)2(PC)2 complexes (PC = orthometalated phosphines, OOCR = carboxylates) with very polarizable ligands, such as aromatic rings directly joined to the rhodium atoms, control chemoselectivity in competitive metal carbene transformations of α-diazo ketones. These catalysts have a mixed set of ligands that allows choosing among a big selection of ligands to gradually affect the electronic and steric properties of the catalyst. Their selectivity depends on the electrophilicity of the ligands and the polarizability of the metalated aromatic rings. Thus, Rh2(OOCR)2(PC)2 compounds [PC = (C6H4)P(CH3)(C6H5), (p-CH3C6H3)P(p-CH3C6H4)2, (C6H4)P(C6H5)2; R = C3F7 or CF3] exhibit an exceptional sele…
Pyrene-benzoylthiophene exciplexes as selective catalysts for the [2+2] cycloaddition between cyclohexadiene and styrenes.
Efficient intramolecular fluorescence quenching in pyrene−benzoylthiophene systems leads to formation of exciplexes. These species interact with 1,3-cyclohexadiene (or styrenes), leading to reactive excited triplexes. The overall process affords [2+2] cross-cycloadducts with an average yield of 57%.