Sergey V. Zheglov

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.

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.

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.

First ligand of phosphite nature based on 5,10,15,20-tetrakis(4-hydroxyphenyl)porphin

Supramolecular asymmetric catalytic systems are formed involving chiral phosphites and amidophosphites underlain by metalloporphyrins [9–15], yet only one chiral phosphite has been prepared with a porphyrin fragment without a metal ion [9]. No published information exists on diamidophosphite porphyrin derivatives, in particular, with asymmetric phosphorus atoms, and also on compounds containing in their composition more than one phosphorus site linked to the porphyrin scaffold.

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.