Alexei A. Shiryaev

Easily Accessible Chiral P,N-Bidentate Aryl Phosphites, Their Complexation and Application in Enantioselective Allylic Alkylation, Sulfonylation and Hydrosilylation

New chiral P,N-hybrid aryl phosphites have been obtained by one-step phosphorylation of amino and imino alcohols. Complexation of the new ligands with [Rh(CO)2Cl]2, [Pd(COD)Cl2] and [Pd(allyl)Cl]2 was found to give chelate complexes [Rh(CO)Cl(η2-P∩N)], [PdCl2(η2-P∩N)] and [Pd(allyl)(η2-P∩N)]+Cl−, respectively. With these new P,N-ligands, up to 82% ee enantioselectivity was achieved in the Pd-catalysed alkylation of ethyl 3-penten-2-yl carbonate with dimethyl malonate, up to 80% ee in the Pd-catalysed sulfonylation of methyl 3-penten-2-yl carbonate with sodium p-toluenesulfinate, and up to 50% ee in the Rh-catalysed hydrosilylation of acetophenone with diphenylsilane. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

An efficient chiral phosphitooxazoline ligand for Pd-catalyzed asymmetric allylic sulfonylation

The new chiral phosphitooxazoline ligand 1 has been synthesized and found to give up to 92% ee in the Pd-catalyzed asymmetric sulfonylation of 1,3-diphenylpropen-2-yl acetate with sodium p-toluenesulfinate.

New oxazoline-containing phosphoramidite ligand for palladium-catalyzed asymmetric allylic sulfonylation

New chiral oxazoline-containing phosphoramidite was synthesized and its complex formation with rhodium(i) and palladium(ii) was examined. The new ligand is a highly efficient chiral inductor (ee up to 92%) in palladium-catalyzed asymmetric sulfonylation of 1,3-diphenylallyl acetate with sodium p-toluenesulfinate.

First P,P*-bidentate phosphine-phosphite-type ligand with a P*-stereocenter in the phosphite moiety: synthesis and application in the Pd-catalyzed asymmetric allylic alkylation

A new P,P*-bidentate phosphine-diamidophosphite bearing an asymmetric phosphorus atom in the 1,3,2-diazaphospholidine ring was obtained. A possibility of its application in the palladium-catalyzed enantioselective allylic substitution was demonstrated. A 70% ee was reached in the alkylation of (E)-1,3-diphenylallyl acetate with dimethyl malonate.

Pd-Catalyzed asymmetric transformations involving P*-mono- and P*,N-bidentate diamidophosphites derived from (2S,3S)-N2,3-dimethyl-N1-phenylpentane-1,2-diamine

The synthesis of new P*-mono- and P*,N-bidentate diamidophosphites, containing 1,3,2-diazaphospholidine rings formed starting from (2S,3S)-N2,3-dimethyl-N1-phenylpentane-1,2-diamine, is described. Comparison of their efficiency in the Pd-catalyzed enantioselective allylation with (E)-1,3-diphenylallyl acetate showed that up to 97% ee was reached in the reaction involving dimethyl malonate as a C-nucleophile. The Pd-catalyzed desymmetrization of N,N′-ditosyl-meso-cyclopent-4-ene-1,3-diol biscarbamate gave up to 61% ee.

Palladium and rhodium-catalyzed enantioselective reactions mediated by pseudodipeptide-based phosphite-type ligand

P*-Chiral diamidophosphite ligand of a 1,3,2-diazaphopholidine series bearing the exocyclic pseudodipeptide fragment was synthesized. The possibility of its application in the palladium- and rhodium-catalyzed asymmetric transformations was demonstrated. This ligand provided up to 84% ee in the Pd-catalyzed alkylation of (E)-1,3-diphenylallyl acetate with dimethyl malonate, up to 56% ee in amination of this substrate with pyrrolidine, and up to 68% ee in alkylation of cinnamyl acetate with ethyl 2-oxocyclohexane-1-carboxylate. In the Rh-catalyzed hydrogenation of (Z)-methyl 2-acetamido-3-phenylacrylate mediated by this ligand, up to 53% ee was achieved.

Diastereomeric bisamidophosphites based on oxalamide 1,3-diol in asymmetric metal complex catalysis

Diastereomeric P*,P*-bisdiamidophosphite ligands of the 1,3,2-diazaphospholidine series bearing an oxalamide moiety have been synthesized. A possibility of their application in palladium- and rhodium-catalyzed asymmetric transformations was demonstrated. In Pd-catalyzed sulfonylation of (E)-1,3-diphenylallyl acetate with sodium p-toluenesulfinate enantioselectivity of up to 57% ee, in alkylation with dimethyl malonate of up to 77% ee, in amination with pyrrolidine of up to 78% ee, and in alkylation of cinnamyl acetate with ethyl 2-oxocyclohexane-1-carboxylate of up to 52% ee, in Rh-catalyzed hydrogenation of (Z-methyl 2-acetamido-3-phenylacrylate of up to 88% ee was achieved. An effi ciency of diastereomeric chirality inducers was compared.

First P,P*-bidentate ligands with P*-chiral diamidophosphite and arylphosphine moieties in Pd-catalyzed asymmetric reactions

GRAPHICAL ABSTRACT ABSTRACT In this mini-review, we have analyzed an application of P*-chiral phosphine-diamidophosphites in Pd-catalyzed asymmetric reactions.