Iminophosphites as new chiral P,N-bidentate ligands

Gavrilov, K. N.; Polosukhin, A. I.; Bondarev, Oleg G.; Korostylev, Andrei I.; Lyubimov, S. E.; Shiryaev, Alexei A.; Starikova, Z. A.; Davankov, V. A.

doi:10.1070/mc2001v011n01abeh001356

“…In particular, the δ P values for complexes 5i and 5l (Table 3) are typical for six-membered palladacycles based on P,N-bidentate phosphites with acyclic phosphorus centres. [11,22] Large coordination shifts ∆δ C , similar to those seen in the rhodium complexes 4i and 4l, were observed for the azomethine carbon atoms in complexes 5i and 5l (Table 2). Two equally intense ν(PdϪCl) bands in the far IR regions of 5i and 5l (Table 3) resulted from the cis configuration of chloro ligands and different trans influences of phosphorus and nitrogen atoms.…”

Section: Introductionsupporting

confidence: 53%

“…CCDC-173440 (4i), -173441 (5i) and -173442 (5l) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html or from the Cambridge Crystallographic Data Centre, 12 [33] [Pd(COD)Cl 2 ], [34] [Pd(allyl)Cl] 2 , [35] amino and imino alcohols 2d, [36] 2f, [37] 2g, [38] 2h, [11] 2l [39] and bis(2,6-dimethylphenyl) chlorophosphite [12] were synthesized as published. The syntheses of compounds 2iϪk and 2m were performed by techniques similar to that reported.…”

Section: Methodsmentioning

confidence: 99%

“…We have recently reported syntheses of several chiral P,N-phosphites with acyclic phosphorus donor centres. [11,12] These gave up to 57% ee in the Pd-catalysed alkylation of 1,3-diphenylpropen-2-yl acetate with dimethyl malonate, and up to 61% ee when 3-phenylpropen-2-yl acetate was used as a substrate. In this article, we describe the synthesis, complexation with Rh I and Pd II precursors and catalytic applications of a new series of P,N-bidentate aryl phosphites bearing distant amino or imino groups.…”

Section: Introductionmentioning

confidence: 95%

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

Gavrilov

¹

,

Bondarev

²

,

Lebedev

³

et al. 2002

Eur. J. Inorg. Chem.

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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) 2 Cl] 2 , [Pd(COD)Cl 2 ] and [Pd(allyl)Cl] 2 was found to give chelate complexes [Rh(CO)Cl(η 2 -P ʝ N)], [PdCl 2 (η 2 -P ʝ N)] and [Pd-(allyl)(η 2 -P ʝ N)] + Cl − , respectively. With these new P,N-ligands, up to 82% ee enantioselectivity was achieved in the [a] The new P,N-bidentate aryl phosphites were synthesized by one-step phosphorylation of the corresponding amino and imino alcohols with bis(2,6-dimethylphenyl) chlorophosphite.They divide into two groups: ligands 3aϪ3f, possessing sp 3 -hybridized nitrogen atoms, and ligands 3gϪ3m, which have sp 2 -hybridized nitrogen atoms. All the compounds 3aϪm are soluble in conventional organic solvents and stable under dry conditions for several months. On treatment with [Rh(CO) 2 Cl] 2 , their neutral carbonyl(chloro)Rh I complexes were obtained.The ν(CO) and 1 J P,Rh parameters in their IR and 31 P NMR spectra act as sensitive indicators, which characterise the mode of complexation of the P,N-ligands and allow the π-acceptor ability of the phosphorus centre and the degree of electronic non-symmetry of the ligands to be estimated. [13Ϫ15] In general, ligands 3aϪ3m give chelate complexes. Thus, the

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“…[134] Due to the nature of the donor atoms, metals which complex to these ligands should experience a highly electronically dissymmetric environment. These ligands were capable of good results in allylic alkylation reactions with both ligands 354 and 355 providing an 82% enantiomeric excess with the dimethylallyl substrate 147.…”

Section: Imidazoline N Donormentioning

confidence: 99%

The Development of Bidentate P,N Ligands for Asymmetric Catalysis

Guiry

¹

,

Saunders

²

2004

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In this review, an attempt is made to systemise the ro √ le which bidentate phosphinamine (P,N) ligands play in asymmetric catalysis. The ligands will be classified, not by the reaction to which their metal complexes have been applied, but by the nature of their donor atoms. In this manner the development of ligand architectural design can be more easily monitored. The asymmetric transformations to which metal complexes of these ligands have been applied include among others, palladium-catalysed allylic substitutions, copper-catalysed 1,4-additions to enones and rhodiumcatalysed hydroboration of vinylarenes. Excellent enantioselectivities, regioselectivities and reactivities have been achieved in each of these processes.

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“…This has made it possible to achieve impressive results in catalytic enantioselective allylation, conjugate addition of organometallic compounds to enones, hydrosilylation and hydrogenation reactions. [11,12] These gave up to 57% ee in the Pd-catalysed alkylation of 1,3-diphenylpropen-2-yl acetate with dimethyl malonate, and up to 61% ee when 3-phenylpropen-2-yl acetate was used as a substrate. ( Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002) structure, normally constructed with the aid of effective chiral inductors such as BINOL, TADDOL, (1R,2R)-1,2-N,NЈ-bis(p-toluenesulfonylamino)-1,2-diphenylethane, (S)-2-(anilinomethyl)pyrrolidine etc.…”

Section: Introductionmentioning

confidence: 99%

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

Gavrilov

¹

,

Bondarev

²

,

Lebedev

³

et al. 2002

Eur. J. Inorg. Chem.

0

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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) 2 Cl] 2 , [Pd(COD)Cl 2 ] and [Pd(allyl)Cl] 2 was found to give chelate complexes [Rh(CO)Cl(η 2 -P ʝ N)], [PdCl 2 (η 2 -P ʝ N)] and [Pd-(allyl)(η 2 -P ʝ N)] + Cl − , respectively. With these new P,N-ligands, up to 82% ee enantioselectivity was achieved in the [a] The new P,N-bidentate aryl phosphites were synthesized by one-step phosphorylation of the corresponding amino and imino alcohols with bis(2,6-dimethylphenyl) chlorophosphite.They divide into two groups: ligands 3aϪ3f, possessing sp 3 -hybridized nitrogen atoms, and ligands 3gϪ3m, which have sp 2 -hybridized nitrogen atoms. All the compounds 3aϪm are soluble in conventional organic solvents and stable under dry conditions for several months. On treatment with [Rh(CO) 2 Cl] 2 , their neutral carbonyl(chloro)Rh I complexes were obtained.The ν(CO) and 1 J P,Rh parameters in their IR and 31 P NMR spectra act as sensitive indicators, which characterise the mode of complexation of the P,N-ligands and allow the π-acceptor ability of the phosphorus centre and the degree of electronic non-symmetry of the ligands to be estimated. [13Ϫ15] In general, ligands 3aϪ3m give chelate complexes. Thus, the

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Iminophosphites as new chiral P,N-bidentate ligands

Cited by 8 publications

References 15 publications

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

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

The Development of Bidentate P,N Ligands for Asymmetric Catalysis

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

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