ortho-palladated α-phenylalkylamines for enantiomeric purity determination of monodentate P∗-chiral phosphines

Dunina, V. V.; Кузьмина, Л. Г.; Kazakova, Marina Yu.; Grishin, Yuri K.; Veits, Yu. A.; Kazakova, E. I.

doi:10.1016/s0957-4166(97)00300-5

Cited by 64 publications

(12 citation statements)

References 45 publications

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“…Cyclopalladated complexes are becoming increasingly important in organic synthesis. − Chiral cyclopalladated derivatives are being used for optical resolution purposes − and for enantioselective catalysis . Many palladacycles have found use in the preparation of metallomesogens, − and some show antitumor activity. , …”

Section: Introductionmentioning

confidence: 99%

Multidonor Ligands. 3. Cyclopalladation of py{SCH₂C(O)R}-2 (py-2 = 2-pyridyl, R = Ph, Me, OMe) through a C(sp³)−H Bond Activation

et al. 1999

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[PdCl2(NCPh)2] reacts with R−carbonylmethylenethiopyridines [py{SCH2C(O)R}-2] to give, depending on the substituent R and the reaction conditions, or the coordination complexes [Pd{py{SCH2C(O)R}-2}2Cl2] (R = Ph, Me, OMe). The latter can be doubly deprotonated by a base (Na2CO3 or NaH) to give dicyclometalated complexes These transmetalate one ligand to [PdCl2(NCPh)2] to give which in turn reacts with (Me4N)Cl or with monodentate ligands L or with MeCN in the presence of AgClO4 to give anionic neutral [R = Ph, L = PPh3, py{SCH2C(O)Ph}-2, tBuNC, NH2CH(Me)Ph, pyridine (py), tetrahydrothiophene (tht); R = Me, L = PPh3, py, tht], or cationic (R = Ph, Me, OMe) complexes, respectively. The latter react with PPh3 or with bidentate ligands to give complexes or [L = PPh3, L2 = N,N,N‘,N‘-tetramethylethylenediamine (tmeda) or 2,2‘-bipyridine (bipy)]. The crystal structures of and have been determined.

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Section: Introductionmentioning

confidence: 99%

Multidonor Ligands. 3. Cyclopalladation of py{SCH₂C(O)R}-2 (py-2 = 2-pyridyl, R = Ph, Me, OMe) through a C(sp³)−H Bond Activation

et al. 1999

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“…Summarizing the results of the synthesis of 2-and 3-phosphine-substituted benzoic esters IV and V (Y = COOCH 3 , COOSiMe 3 ) we can conclude that reactions (1) and (2) are hardly suitable in this case. Byprocesses induced by the evolving bromo(iodo)trimethylsilanes practically exclude the possibility of synthesis of tertiary phosphines IV with Y = COOR.…”

Section: äääääääääääämentioning

confidence: 83%

“…In view of these results, we primarily studied the cross coupling of bis-silylphosphines IIa and IIb with bromide IIIa (Y = 3-CF 3 ) which was expected to be the most resistant to bromo-and especially iodotrimethylsilane evolved upon prolonged heating of the components of reaction (2). Reactions (1) and (2) were carried out in sealed ampules with magnetic stirring and thermostating under the conditions shown in Table 1, without solvent, and in the presence of 335 mol % of PdCl 2 (Ph 3 P) 2 or RdCl 2 .…”

Section: äääääääääääämentioning

confidence: 99%

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Synthesis of Sterically Hindered Secondary and Tertiary Alkyl(Aryl)Phosphines

2005

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Cross coupling of silylphosphines with 2-halobenzenecarboxylates or 2-halophenyl ethers, catalyzed with zero-valent palladium complexes can not be used as a procedure for preparing sterically hindered tertiary phosphines. The latter compounds can be successfully prepared by means of phosphorylation of corresponding o-lithiated derivatives.In [1], a procedure for preparing secondary alkyl-(aryl)phosphines of the general formula RArPH containing electron-donor and electron-acceptor substituents in the aromatic ring have been proposed. This procedure is based on cross coupling of alkyl-(trimethylsilyl)phosphines with corresponding aryl halides in the presence of catalytic amounts of zerovalent palladium.In this work we have studied the cross coupling of trimethylsilyl derivatives of secondary phosphines R 1 R 2 PSiMe 3 Ia and Ib [R 1 = i-Pr, R 3 = tert-Bu (a); R 1 = tert-Bu, R 2 = Ph (b)] and also of bis-silylated primary phosphines RP(SiMe 3 ) 2 IIa and IIb [R = i-Pr ÄÄÄÄÄÄÄÄÄÄÄÄ (a); R = tert-Bu (b)] with various aryl halides YC 6 H 4 Hlg III [reactions (1) and (2)] with the purpose to establish the utility of the above procedure for preparing tertiary alkyl(aryl)phosphines R 1 R 2 PC 6 H 4 Y IV and RP(C 6 H 4 Y) 2 V with secondary and tertiary alkyl groups and a series of o-and m-substituents in the aromatic ring. Bulky radicals in phosphines IV and V, including o-substituted in the aromatic ring, were chosen to impart configurational stability to racemic tertiary phosphines which we proposed to resolve into optical antipodes [2]. Substituents containing alkoxycarbonyl groups were introduced to render the synthesized phosphine ligands water-soluble after hydrolysis. R 1 R 2 PSiMe 3 + 4 c = Y Hlg 7777776 3Me 3 SiHlg 235 mol% Pd(0), to 4 c = Y PR 1 R 2 I III IV R(PSiMe 3 ) 2 + 2III 7777776 3Me 3 SiHlg 235 mol% Pd(0), to 4 c = Y PR 2 V II (1) (2) ÄÄÄÄÄÄÄÄÄÄÄÄIt was previously reported that the aromatic functionally substituted tertiary phosphines are successfully prepared by cross coupling of bromo(iodo)arenes III with diphenyl(trimethylsilyl)phosphine [3] and even with diphenylphosphine [4,5], whereas tertiary phosphines with bulky alkyl groups and functional groups in the aromatic ring were not obtained.Preliminary experiments showed [1] that the synthesis of tertiary phosphines by reaction (2) requires much more rigid conditions (1303140oC) than the synthesis of secondary phosphines (503100oC), and the slowest reactions are observed with o-substituted haloarenes III. In view of these results, we primarily studied the cross coupling of bis-silylphosphines IIa and IIb with bromide IIIa (Y = 3-CF 3 ) which was expected to be the most resistant to bromo-and especially iodotrimethylsilane evolved upon prolonged heating of the components of reaction (2). Reactions (1) and (2) were carried out in sealed ampules with

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“…Chiral CPCs are very successfully used in asymmetric synthesis, both as the original matrix [2][3][4][5][6][7] and as catalysts [8][9][10][11][12]. They have been used in NMR studies as shifting reagents [13][14][15] and as effective resolution agents [16][17][18]. This is especially significant for obtaining enantiopure phosphines, which are efficient ligands for asymmetric catalysis of transition metal complexes.…”

Section: Introductionmentioning

confidence: 99%

Chiral palladium complexes based on derivatives of benzylamine and 2α-hydroxypinan-3-one

Zalevskaya¹,

Gur’eva²,

Фролова³

et al. 2010

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Synthesized and characterized new chiral palladium complexes, some of which contain asymmetric donor nitrogen atom. Nitrogen-containing derivatives (+)-and (-)-2α-hydroxypinan-3-one-(1R,2R,5R)-3-(benzylimino)-2,6,6-trimethylbicyclo[3.1.1]heptane-2-ol (HL 1), (1S,2S,3S,5S)-3-(benzylamino)-2,6, 6-trimethylbicyclo[3.1.1]heptane-2-ol (HL 2), (1R,2R,5R)-3-((S)-α-methylbenzylimino)-2,6,6-trimethylbicyclo[3.1.1]heptane-2-ol (HL 3), (1R,2R,3R,5R)-3-((S)-α-methylbenzylamino)-2,6,6-trimethylbicyclo[3.1.1]heptane-2-ol (HL 4)-were studied as optically active ligands.

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ortho-palladated α-phenylalkylamines for enantiomeric purity determination of monodentate P∗-chiral phosphines

Cited by 64 publications

References 45 publications

Multidonor Ligands. 3. Cyclopalladation of py{SCH₂C(O)R}-2 (py-2 = 2-pyridyl, R = Ph, Me, OMe) through a C(sp³)−H Bond Activation

Multidonor Ligands. 3. Cyclopalladation of py{SCH₂C(O)R}-2 (py-2 = 2-pyridyl, R = Ph, Me, OMe) through a C(sp³)−H Bond Activation

Synthesis of Sterically Hindered Secondary and Tertiary Alkyl(Aryl)Phosphines

Chiral palladium complexes based on derivatives of benzylamine and 2α-hydroxypinan-3-one

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ortho-palladated α-phenylalkylamines for enantiomeric purity determination of monodentate P∗-chiral phosphines

Cited by 64 publications

References 45 publications

Multidonor Ligands. 3. Cyclopalladation of py{SCH2C(O)R}-2 (py-2 = 2-pyridyl, R = Ph, Me, OMe) through a C(sp3)−H Bond Activation

Multidonor Ligands. 3. Cyclopalladation of py{SCH2C(O)R}-2 (py-2 = 2-pyridyl, R = Ph, Me, OMe) through a C(sp3)−H Bond Activation

Synthesis of Sterically Hindered Secondary and Tertiary Alkyl(Aryl)Phosphines

Chiral palladium complexes based on derivatives of benzylamine and 2α-hydroxypinan-3-one

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Multidonor Ligands. 3. Cyclopalladation of py{SCH₂C(O)R}-2 (py-2 = 2-pyridyl, R = Ph, Me, OMe) through a C(sp³)−H Bond Activation

Multidonor Ligands. 3. Cyclopalladation of py{SCH₂C(O)R}-2 (py-2 = 2-pyridyl, R = Ph, Me, OMe) through a C(sp³)−H Bond Activation