0000000000563791
AUTHOR
Maryse Gouygou
Modular Phosphole-Methano-Bridged-Phosphine(Borane) Ligands. Application to Rhodium-Catalyzed Reactions
The synthesis of the phospholyl(phosphinoborane)methane air- and moisture-stable hybrid ligands 4a–f, starting from 1-phenylphospholes 1a–d, was performed via P–C bond coupling on the methano bridge. Two strategies were investigated, according to the phospholyl moiety used as a nucleophilic or an electrophilic reagent. In the first pathway, the phospholyl anions react with the easily available (chloromethyl)diphenylphosphine–borane 3 to afford ligands 4a–d in 29–67% isolated yields. In the second pathway, the phospholyl(dicyclohexylphosphinoborane)methane ligands 4e,f were synthesized in 18–23% yields, through a nucleophilic substitution on the cyanophosphole. Removal of the BH3 moiety on 4…
First Dibenzophospholyl(diphenylphosphino)methane−Borane Hybrid P−(η2-BH3) Ligand: Synthesis and Rhodium(I) Complex
The first dibenzophospholyl(diphenylphosphino)methane−borane hybrid ligand has been prepared from a Pd-catalyzed reaction of (chloromethyl)diphenylphosphine−borane with the dibenzophospholyl anion. This borane precursor is readily synthesized using a promising new reaction of diphenylphosphine−borane with dichloromethane, under phase transfer catalysis (PTC) conditions. The dibenzophospholyl(diphenylphosphino)methane−borane acts as a chelating P−(η2-BH3) ligand to afford an air-stable Rh(I) complex. The X-ray crystal structure of this complex shows complexation of both benzophospholyl and borane moieties.
Phospholylmethano P-chirogenic-phosphine-borane as P-(η2-BH3)-chelating ligands of rhodium (I): Synthesis, characterization and asymmetric hydrogenation
International audience; The stereoselective synthesis of new phospholylmethano P-chirogenic-phosphine-borane was achieved by P-C bond formation of the bridge, using electrophilic or nucleophilic P*-building blocks. These P1CH2P2*.BH3 ligands behaved as chelating (κ1-P1)-(η2-BH3) entities towards the cationic rhodium(I) centre. The resulting chiral rhodium complexes were tested in asymmetric rhodium catalyzed hydrogenation of methyl 2-(acetamido)acrylate.
CCDC 2034046: Experimental Crystal Structure Determination
Related Article: Christine Salomon-Bertrand, J��r��me Bayardon, Hugo Laur��ano, Sylvain Jug��, Jean-Claude Daran, Maryse Gouygou|2021|J.Organomet.Chem.|938|121753|doi:10.1016/j.jorganchem.2021.121753