V. K. Gavrilov

Palladium-catalyzed enantioselective allylation in the presence of phosphoramidites derived from (Sa)-3-SiMe3-BINOL, (R,S)-semi-TADDOL, and (R,R)-TADDOL

Novel P*- and P-monodentate phosphoramidites of a 1,3,2-dioxaphosphepine series were derived from (Sa)-3-trimethylsilyl-BINOL, (R,S)-semi-TADDOL, and (R,R)-TADDOL. Catalytic performance of the synthesized compounds were examined in the Pd-catalyzed asymmetric allylic substitution of (E)-1,3-diphenylallyl acetate: the reaction with dimethyl malonate gave up to 92% ee. The effects of additives of 5,10,15,20-tetraphenylporphyrin and its metal complexes on conversion and enantioselectivity were studied.

Chiral amido- and diamidophosphites with a peripheral pyridine ring in Pd-catalyzed asymmetric allylation

New chiral amidophosphite and diamidophosphite ligands with exocyclic pyridyl-containing substituents were obtained. Their efficiency in the Pd-catalyzed enantioselective allylic substitution was compared: in the sulfonylation of (E)-1,3-diphenylallyl acetate with sodium p-toluenesulfinate, the ee can reach 77%; its alkylation with dimethyl malonate and amination with pyrrolidine gave up to 80% and 74% ee, respectively. The asymmetric alkylation of cinnamyl acetate with ethyl 2-oxocyclohexanecarboxylate can provide to 68% ee. The complexation of zinc(ii) 5,10,15,20-tetraphenylporphyrinate with diamidophosphite ligand and its influence on conversion and enantioselectivity of the process were studied.

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.

Chiral phosphite-type ligands based on ((4 R ,5 R )-2,2-dimethyl-1,3-dioxolane-4,5-diyl)bis(diphenylmethanol) (( R , R )-TADDOL) with peripheral arylamino groups

New phosphite and amidophosphite inductors of chirality were obtained based on ((4R,5R)-2,2-dimethyl-1,3-dioxolane-4,5-diyl)bis(diphenylmethanol) ((R,R)-TADDOL) containing arylamino groups in the exocyclic substituents. Their use in the palladium-catalyzed enantioselective alkylation of (E)-1,3-diphenylallyl acetate with dimethyl malonate gave the ee value up to 98%.

Diamidophosphite based on (1R,2R)-1,2-bis(3-hydroxybenzamido)cyclohexane in Pd-catalyzed enantioselective allylation

Diamidophosphite ligand bearing (1R,2R)-1,2-bis(3-hydroxybenzamido)cyclohexane fragment and stereogenic phosphorus atoms in the 1,3,2-diazaphopholidine cycles was synthesized. Catalytic performance of this ligand was evaluated in asymmetric allylic substitution. In the reactions involving (E)-1,3-diphenyl allyl acetate as a substrate, up to 94% ee in alkylation with dimethyl malonate and up to 68% ee in amination with pyrrolidine was achieved in the presence of this ligand.

Phosphorylated (S)-tert-leucinol isophthalic diamide as a ligand for Pd-catalyzed asymmetric allylic substitution

O-Phosphorylation of N,N’-(isophthaloyl)di-(S)-tert-leucinol with (5S)-2-chloro-3-phenyl-1,3-diaza-2-phosphabicyclo[3.3.0]octane afforded bidentate phosphite-type ligand. This ligand provided 93% ee in Pd-catalyzed enantioselective allylation of (E)-1,3-diphenylallyl acetate, and 55% ee in alkylation of cinnamyl acetate with ethyl 2-oxocyclohexane-1-carb-oxylate.

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.

Phosphine-phosphoramidites with 2-(diphenylphosphino)-ethylamine or N-methyl-2-(diphenylphosphino)ethylamine fragments

GRAPHICAL ABSTRACT ABSTRACT New phosphine-phosphoramidite ligands based on (R)-[1,1′-binaphthalene]-2,2′-diol, containing exocyclic fragment of 2-(diphenylphosphanyl)ethan-1-amine or 2-(diphenylphosphanyl)-N-methylethan-1-amine were obtained and characterized by 31P, 1H, and 13C NMR spectroscopy.

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.