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

Gavrilov, K. N.; Bondarev, Oleg G.; Lebedev, R. V.; Shiryaev, Alexei A.; Lyubimov, S. E.; Polosukhin, A. I.; Grintselev-Knyazev, Gennady V.; Lyssenko, Konstantin А.; Moiseev, S. K.; Ikonnikov, Nikolay S.; Калинин, В. Н.; Даванков, В. А.; Korostylev, Andrei; Gais, Hans‐Joachim

doi:10.1002/1099-0682(200206)2002:6<1367::aid-ejic1367>3.0.co;2-f

Cited by 34 publications

(24 citation statements)

References 35 publications

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“…This is not observed for complexes 8a, 9b and 10 either because of the fast interconversion of the isomers or due to the absence of one of the isomers. 22 It should be mentioned that compounds 8a and 8b, 9a and 9b and 10 are photosensitive. Thus, even a shortterm exposure to light of their chloroform solutions resulted in precipitation of a black solid and in the appearance of additional signals in the d P 110-130 and 7-33 ppm regions of their 31 P NMR spectra.…”

Section: Resultsmentioning

confidence: 82%

“…22 According to the 1 J(P, Rh) and m(CO) parameters of 6a and 6b and 7a and 7b, diamidophosphites 4a and 4b, and 5a and 5b occupy an intermediate position between phosphines and phosphoramidites in a spectrochemical range of organophosphorus ligands. 23,24 Besides, 4a and 4b, and 5a and 5b have practically identical p-acceptor and r-donor properties, for 1 J(P, Rh) and m(CO) parameters of their chlorocarbonyl rhodium complexes are rather close.…”

Section: Resultsmentioning

confidence: 99%

“…21,30 Rhodium complexes 6a and 6b, and 7a and 7b were synthesized for 31 P NMR and IR experiments in chloroform analogously to the known procedures. 22 Syntheses of cationic palladium complexes 8a and 8b, 9a and 9b and 10 were performed by techniques similar to those reported earlier. 31 Starting substrate 11 and complex [Pd(allyl)Cl] 2 for catalysis were synthesized as published.…”

Section: Generalmentioning

confidence: 99%

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Cymantrene-based iminodiamidophosphites: the first phosphite-type ligands with planar chirality

Gavrilov

Tsarev

Konkin

et al. 2005

Tetrahedron: Asymmetry

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Section: Resultsmentioning

confidence: 82%

Section: Resultsmentioning

confidence: 99%

Section: Generalmentioning

confidence: 99%

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Cymantrene-based iminodiamidophosphites: the first phosphite-type ligands with planar chirality

Gavrilov

Tsarev

Konkin

et al. 2005

Tetrahedron: Asymmetry

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“…The molecular structure shows the rhodium atom to be in a square-planar geometry surrounded by the imino nitrogen atom trans to the carbonyl ligand and the chloro ligand trans to phosphorus. The geometrical parameters around the rhodium atom are comparable to those found in the analogous complexes [Rh(PyP)(CO)Cl] (PyP = 1-(2-diphenylphosphino)ethylpyrazole) [25], [Rh(P-N)(CO)Cl] (P-N = diphenylphosphino(phenyl pyridine-2-yl methylene)amine) [26] and [Rh(P-N*)(CO)Cl] (P-N* = (2S, 3S)-2-{4-(dimethylamino)benzylideneamino} + -3-methylpentyl bis (2,6-dimethylphenyl) phosphite) [27]. The formation of a six-membered chelate ring imposes distortion around the rhodium atom.…”

Section: Introductionmentioning

confidence: 99%

Rhodium(I) iminophosphine poly(propyleneimine) dendrimers: Synthesis, characterization and molecular structure of a mononuclear analogue

Antonels¹,

Therrien²,

Moss³

et al. 2009

Inorganic Chemistry Communications

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a b s t r a c tFirst (G1)-and second-generation (G2) poly(propyleneimine) (PPI) dendrimers were reacted with 2-(diphenylphosphino)benzaldehyde, to form iminophosphine-functionalised dendritic ligands (1, 2). The reaction of the dimeric precursor [RhCl(CO) 2 ] 2 with the heterobidentate dendritic ligands 1, 2 gave the corresponding rhodium(I) complexes (3, 4). There has been recent interest in the chemistry of polydentate ligands, especially those which combine ''soft" and ''hard" donor atoms [11]. The most used hemilabile ligands are the P,N-donor bidentate ligands, combining the distinct behaviour of a soft phosphorus atom which coordinates very strongly to a soft metal centre (e.g. palladium) and a hard nitrogen donor which is weakly bound. Non-rigid ligands, such as the widely studied iminophosphines, often act as chelating ligands that easily form five-or six-membered chelate rings. Iminophosphines display versatile coordination behaviour and are potentially hemilabile, making them useful for a variety of homogeneous processes, such as, C-C coupling reac- [16]. The steric and electronic properties of such ligands can also be fine-tuned and this can have a huge effect on the kinetics and thermodynamics of a chemical reaction [17].Examples of metallodendritic chelating heterobidentate complexes are rare. For metallodendrimers containing P and N donor atoms, many transition metals are coordinated in a P-monodentate or N-monodentate fashion. In this communication, we report on the synthesis of first-and second-generation chelating, heterobidentate [P, N] iminophosphine dendritic ligands and their coordination chemistry with a Rh(I) precursor. The molecular structure of a mononuclear analogue is also presented and discussed.The synthesis of the first-and second-generation iminophosphine-functionalised dendritic ligands 1 and 2 ( Fig. 1) [19] was achieved by a Schiff-base condensation reaction of the commercially available DAB-dendr-(NH 2 ) n with 2-diphenylphosphinobenzaldehyde. Screttas et al. first reported the synthesis of a third generation iminophosphine dendritic ligand based on a poly(propyleneimine) scaffold [18]. These dendritic P,N ligands were used in situ in the presence of palladium acetate in the Heck cross-coupling of p-anisyl bromide with styrene.The dendritic ligands (1, 2) were isolated as pale yellow solids in moderate yields (65-68%). These compounds were characterized by elemental analysis (C, H, N) Published in Inorganic Chemistry Communications 12, issue 8, 716-719, 2009 which should be used for any reference to this work 1imine moiety are observed as a triplet around 3.69 ppm, for 1 and 2. The appearance of a singlet at ca. 8.37 ppm, assigned to the imine proton (-CH 2 N@CH-CH 2 -) establishes that the condensation reaction has occurred. As was the case for Screttas and co-workers, it is important to consider syn and anti isomerism about the imine double bond [18]. One resonance is noted for the imine proton in both ligands, assigned to the trans isomer for steric reasons. The 31 P{ 1 H} ...

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“…10 and references cited therein) the pronounced π withdrawing ability of ligand 3 typical of aryl phosphites, which is substantial for attaining high chemical and optical yields in some areas of asymmetric catalysis. 2,3 Note that complex 5 is stable in solution (NMR data).…”

Section: Resultsmentioning

confidence: 99%

A first P,N-bidentate phosphite with a chiral ketimine fragment. Catalytic properties of its RhI and PdII complexes in comparison with those of phosphine analogs

et al. 2004

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A chiral P,N bidentate aryl phosphite ligand containing peripheral (R) (+) camphor derived ketimine and its rhodium(I) and palladium(II) chelate complexes were synthesized for the first time. These compounds were found to be suitable for asymmetric allylic substitution. The Pd catalyzed sulfonylation of 1,3 diphenylallyl acetate with sodium p toluenesulfinate gave the product in 73% ee; in the alkylation of the same substrate with dimethyl malonate, the ee was 94%. These ee values are higher than the enantioselectivity achieved with the known phosphine analogs.Imino phosphines constitute an important group of chiral P,N bidentate ligands for asymmetric catalysis by metal complexes. 1-3 The vast majority of such compounds contain an aldimine fragment, whereas systems with ketimine units are fairly uncommon. 4-6 Since recently, imino phosphites have been successfully used in enan tioselective catalysis because of their high π acidity, resis tance to oxidation, synthetic accessibility, and low cost (see Refs 3 and 7 and references cited therein and Ref. 8). However, all these ligands contain a peripheral aldimine group; no phosphite with a ketimine fragment has been documented to date. In the present work, a first chiral aryl phosphite containing a ketimine substituent based on (R) (+) camphor was synthesized and successfully used in Pd catalyzed asymmetric allylation. Results and DiscussionA new P,N bidentate chiral aryl phosphite was easily obtained by phosphorylation of camphor N (o hydroxy phenyl)imine (1) with accessible reagent 2 (Scheme 1).It should be noted that imino phosphite 3 is stable when stored in a dry atmosphere. For instance, the 31 P NMR spectrum of compound 3 recorded several months after it has been synthesized shows no signals for decomposition products. In addition, the starting reagents, including (R) (+) camphor, are inexpensive. As regards the complexation character, ligand 3 is a typical chelating agent. In particular, its reactions with [Pd(All)Cl] 2 in the presence of AgBF 4 and with [Rh(CO) 2 Cl] 2 gave cationic and neutral metal chelates 4 and 5 with cis orientation of the P and N atoms (Scheme 2). Scheme 1

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

Cited by 34 publications

References 35 publications

Cymantrene-based iminodiamidophosphites: the first phosphite-type ligands with planar chirality

Cymantrene-based iminodiamidophosphites: the first phosphite-type ligands with planar chirality

Rhodium(I) iminophosphine poly(propyleneimine) dendrimers: Synthesis, characterization and molecular structure of a mononuclear analogue

A first P,N-bidentate phosphite with a chiral ketimine fragment. Catalytic properties of its RhI and PdII complexes in comparison with those of phosphine analogs

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