Synthesis of Chiral Heterocyclic Phosphines for Application in Asymmetric Catalysis

Holz, Jens; Gensow, M.‐N.; Zayas, Odalys; Börner, Armin

doi:10.2174/138527207779316525

Cited by 56 publications

(32 citation statements)

References 142 publications

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“…Accompanied by the wide applicability of optically active phosphorous compounds for asymmetric reactions, studies on P-chirogenic optically active phosphorous compounds and their application in asymmetric synthesis have also been the subject of much interest. 4 However, optically active P-chirogenic ferrocene-fused phospholes have not been reported so far, although the ferrocene back bone was known to provide effective enantiocontrol environment for a wide variety of asymmetric reactions. For instance, reactions of chiral phosphinates and phosphorous-borane complexes with organolithiums and Grignard reagents result in nucleophilic substitution to afford appropriate new P-chirogenic phosphorous compounds.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Optically Active P-Chirogenic Ferrocene-Fused Benzophosphole by Diastereoselective Intramolecular Cyclization of Phosphanylferrocene Derivatives

Kurita¹,

Hagiwara²,

Danjo³

et al. 2009

HETEROCYCLES

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A novel optically active P-chirogenic ferrocene-fused benzophosphole, (S Fc ,R P )-4-phenylbenzo[b]ferroceno[d]phosphole, was synthesized by diastereoselective intramolecular cyclization of (S Fc )-1-(diphenylphosphanyl)-2-(2-lithiophenyl)ferrocene intermediates in two routes. The geometry of the new P-chirogenic ferrocenophosphole including absolute configuration of the phosphorous was disclosed by single crystal X-ray analysis of the palladium complex derived from the reaction of the phosphole with di-μ-dichloro-bis{2-[(dimethylamino)methyl]phenyl-C 1 ,N}dipalladium (II).

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Section: Introductionmentioning

confidence: 99%

Synthesis of Optically Active P-Chirogenic Ferrocene-Fused Benzophosphole by Diastereoselective Intramolecular Cyclization of Phosphanylferrocene Derivatives

Kurita¹,

Hagiwara²,

Danjo³

et al. 2009

HETEROCYCLES

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“…Phosphine oxides and phosphines having a chiral phosphorus atom, including optically active compounds, are successfully used as ligands for metalcomplex catalysts in organic and asymmetric synthesis [1][2][3]; some derivatives are known as pesticides and biologically active substances [4]. However, more extensive application of these compounds is seriously limited due to complexity of methods for the preparation of phosphine oxides and phosphines with three different substituents, especially with those containing additional functional groups.…”

Section: Short Communicationsmentioning

confidence: 99%

“…However, more extensive application of these compounds is seriously limited due to complexity of methods for the preparation of phosphine oxides and phosphines with three different substituents, especially with those containing additional functional groups. Taking into account continuously growing demands for such compounds, development of accessible procedures for their synthesis remains to be important (see, e.g., [3][4][5][6][7]). Most known procedures require the use of expensive reagents and are complex and laborious; isolation of intermediate and final products is often difficult.…”

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confidence: 99%

“…of ABX spin system, 2 J AB = 14.9, 3 J PH = 9.2 Hz), 3.57 d.d (1H, CH 2 , part B of ABX spin system, 2 J AB = 14.9, 3 J PH = 14.9 Hz), 7.12 m (1H, 3-H,3 J HH = 7.5-7.3 Hz), 7.17 m (2H, 2-H, 3 J HH = 7.5-7.8, 7.3-7.5 Hz), 7.25 m (2H, 1-H, 3 J HH = 7.5-7.8 Hz), 7.42 m (2H, 5-H, 5 J PH = 2.5, 3 J HH = 8.5, 7.4 Hz), 7.47 m (1H, 6-H, 3 J HH = 7.4, 4 J = 1.2 Hz), 7.71 m (2H, 4-H, 3 J PH = 9.8, 3 J HH = 8.5, 4 J HH = 1.3 Hz). 31 P-{ 1 H} NMR spectrum: δ P 51.3 ppm.…”

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confidence: 99%

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A simple synthetic approach to unsymmetrically substituted (γ-oxoalkyl)phosphine oxides

et al. 2010

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SHORT COMMUNICATIONSPhosphine oxides and phosphines having a chiral phosphorus atom, including optically active compounds, are successfully used as ligands for metalcomplex catalysts in organic and asymmetric synthesis [1][2][3]; some derivatives are known as pesticides and biologically active substances [4]. However, more extensive application of these compounds is seriously limited due to complexity of methods for the preparation of phosphine oxides and phosphines with three different substituents, especially with those containing additional functional groups. Taking into account continuously growing demands for such compounds, development of accessible procedures for their synthesis remains to be important (see, e.g., [3][4][5][6][7]). Most known procedures require the use of expensive reagents and are complex and laborious; isolation of intermediate and final products is often difficult. Either racemates are obtained with subsequent optical resolution or stereoselective syntheses are necessary.We proposed a new and simple synthetic approach to unsymmetrically substituted phosphine oxides containing an oxo group as additional functional substituent in the γ-position with respect to the phosphorus atom. This approach is based on the reaction of accessible phosphorus-containing heterocycles having two P-C bonds, in particular 2-alkyl(aryl)-3,3,5-trimethyl-2,3-dihydro-1,2λ 5 -oxaphosphole 2-oxides like I [8][9][10][11], with Grignard compounds. Hydrolysis of the reaction mixture gives targeted (1-methyl-4-oxopent-2-yl)phosphine oxides II in more than 95% yield. Due to specific structure of the initial dihydrophosphole oxides (they possess one exo-and one endocyclic P-C bond and reactive endocyclic P-O bond), the third P-C bond is formed with high chemoselectivity with no any side process. As a result, the products are formed in high yields and with high purity. The structure of phosphine oxides II thus obtained was confirmed by IR, 1 H, 31 P, and 13 C NMR, and mass spectra. 4-[Ethyl(methyl)phosphoryl]-4-methylpentan-2-one (IIa).Compound Ia, 5.7 g (35.6 mmol), was added dropwise to the Grignard compound prepared according to standard procedure from 1.3 g (54.2 mmol) of magnesium and 4.1 ml (5.9 g, 54.2 mmol) of ethyl bromide in 100 ml of diethyl ether. When the addition was complete, the mixture was heated to the boiling point under vigorous stirring over a period of 1 h, cooled to 20°C, and neutralized under vigorous stirring at the boiling point by adding in succession 30 ml of water and 5 ml of hydrochloric acid. The organic phase was separated, the aqueous phase was extracted with methylene chloride (2 × 100 ml), the extracts were combined with the organic phase, the solvent was distilled off, and the residue was dried under reduced pressure (12 mm) at 100°C. Yield 6.6 g (98%), light brown oily substance. IR spectrum, cm -1 : I, R 1 = Me (a), Ph (b); II, R 1 = Me, R 2 = Et (a), Pr (b); R 1 = Ph, R 2 = PhCH 2 (c).

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“…[21] Herein, we compare the results obtained in the Rh-catalyzed asymmetric hydrogenation of unsaturated lactic acid precursors using several bisphospholane ligands. [22] The main focus is the use of PC as an environmentally benign solvent.…”

Section: Introductionmentioning

confidence: 99%

Rh‐Catalyzed Asymmetric Hydrogenation of Unsaturated Lactate Precursors in Propylene Carbonate

et al. 2008

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The asymmetric hydrogenation of alpha-acetoxy acrylates to O-acetyl lactates with Rh catalysts based on chiral bisphospholane ligands was investigated in propylene carbonate (PC) as "green" solvent. In contrast to DuPHOS-type ligands, catASium M ligands lead to full conversion of the substrate in PC and induce excellent enantioselectivities for ethyl ester and methyl ester substrates (>98 %). Moreover, the undesired opening of the maleic anhydride moiety of the catASium M ligand observed in MeOH can be prevented under these conditions. The chiral product can be easily separated from the carbonate solvent by distillation. In this way, an ecologically benign process for the production of enantiopure lactic acid derivatives was established which offers a highly efficient catalytic transformation in a green solvent under mild conditions (1-10 bar H(2)).

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Synthesis of Chiral Heterocyclic Phosphines for Application in Asymmetric Catalysis

Cited by 56 publications

References 142 publications

Synthesis of Optically Active P-Chirogenic Ferrocene-Fused Benzophosphole by Diastereoselective Intramolecular Cyclization of Phosphanylferrocene Derivatives

Synthesis of Optically Active P-Chirogenic Ferrocene-Fused Benzophosphole by Diastereoselective Intramolecular Cyclization of Phosphanylferrocene Derivatives

A simple synthetic approach to unsymmetrically substituted (γ-oxoalkyl)phosphine oxides

Rh‐Catalyzed Asymmetric Hydrogenation of Unsaturated Lactate Precursors in Propylene Carbonate

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