Phosphinites synthesis

Agbossou E., Carpentier J. E. Hapiot E., Suisse I., Mortreux A. The Aminophos-phine-Phosphinites and Related Ligands Synthesis, Coordination Chemistry and Enantioselective Catalysis Coord. Chem. Rev. 1998 I78-I80 1615-1645 Keywords stereoselective Diels-Alder reaction catalysts, aminophosphine-phosphinites, enantioselective catalysts... 

Scheme 2 Synthesis of dipeptido phosphinite ligands 1-4 and corresponding metal complexes, 5-12 (i) ClPPh2, CH2C12, Et3N, DMAP (ii) (BzCN)2MC12, CH2C12, M = Pt, Pd.

Trofimov, B.A. Gusarova, N.K., Malysheva, S.F., Rakhmatulina, T.N., Voronkov, M.G., Dmitriev, V.I., and Shaikhudinova, S.I., Superbase-induced generation of phosphide and phosphinite ions as applied in organic synthesis, Phosph., Sulf., Silic. Relat. Elem., 55, 271, 1991. 

The directed synthesis of biaryls can be achieved using rhodium-based catalysts along with a phosphinite co-ligand (Equation (143)). 

Scheme 33.4 One-step synthesis of aminophosphine phosphinite bidentate ligands.

SYNTHESIS AND APPLICATION OF PHOSPHINITE OXAZOLINE IRIDIUM COMPLEXES FOR THE ASYMMETRIC HYDROGENATION OF ALKENES... 

Certain chiral phosphinite or aminophosphine ligands are also useful for amino acid synthesis. Hydrogenation with a CYCPHOS-Rh complex occurs rapidly to produce high optical yields. The efficacy of this reaction is ascribed to the flexibility of the ligand, which speeds the reaction and gives a fixed chelate ring conformation (26). 

Chiral bis(phosphinites) derived from (2/J,51 )-2,5-di(hydroxymethyl)tetrahydrothiophene have been prepared (Equation 73). These ligands have been used in the synthesis of rhodium complexes from Rh(COD)2X (COD = cyclooctadiene X = OTf, SbF6) and tested in the asymmetric hydrogenation of methyl a-acetamidocinna-mate. A maximum of 55% enantioselectivity was observed <19980M4976>. 

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