Kinetic Resolution of Phosphines and Phosphine Oxides with Phosphorus Stereocenters by Hydrolases

Serreqi, Alessio N.; Kazlauskas, Romas J.

doi:10.1021/jo00104a015

Cited by 38 publications

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“…[7,8] ), no such literature example can be found in the case of P-chiral hydroxyphosphoryl analogues (for an example of a kinetic resolution of b-hydroxyphosphines and phosphine oxides, thus with the hydroxy group located at a distance of three bonds from the stereogenic phosphorus atom, with E up to 81, see ref. [9] ). To check whether the same procedure, as for the transformation of the sulfoxide 1, will be effective for the phosphoryl analogues, we decided to investigate both the enzymatic kinetic resolution of racemic and the desymmetrization of prochiral phosphine oxides, bearing the reacting hydroxy group distant from the stereogenic or prostereogenic phosphorus atom by four bonds.…”

Section: Introductionmentioning

confidence: 99%

Enzymatic Synthesis of Enantiopure Precursors of Chiral Bidentate and Tridentate Phosphorus Catalysts

et al. 2011

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Abstract:The Candida antarctica lipase (CAL-B)-catalyzed acetylation of racemic 2-hydroxy-phenylphosphine oxide, performed in diethyl ether, led to kinetic resolution with an unusually high enantioselectivity (E = 3000). The CAL-B-mediated desymmetrization of prochiral bis(2-hydroxymethylphenyl)methylphosphine oxide gave, via its enantioselective monoacetylation, the corresponding monoacetate in 80% yield and with ee > 98%. The latter transformation allowed us to efficiently transform the prochiral substrate into the enantiomerically pure product in one single step. In both cases the stereogenic or prostereogenic phosphorus atom and the reacting hydroxy oxygen are distant from each other by four bonds. The absolute configurations of all the products were determined by a chemical correlation and X-ray analysis. The products will be used as enantiopure substrates in the preparation of a variety of chiral organophosphorus ligands/catalysts for asymmetric synthesis.

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Section: Introductionmentioning

confidence: 99%

Enzymatic Synthesis of Enantiopure Precursors of Chiral Bidentate and Tridentate Phosphorus Catalysts

et al. 2011

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“…Although there are fewer examples, this chiral aryl rule may also apply to CRL. For the sulfoxides lb, 4b, and Sb, CRL was less enantioselective than CE; however, for the phosphines and phosphine oxides, CRL was more enantioselective (34).…”

Section: Discussionmentioning

confidence: 90%

“…The second group of substrates comprises the sulfoxides resolved in this paper and the related phosphines and phosphine oxides resolved previously (34), Fig. 3b.…”

Section: Front View Side Viewmentioning

confidence: 80%

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Kinetic resolution of sulfoxides with pendant acetoxy groups using cholesterol esterase: substrate mapping and an empirical rule for chiral phenols

Serreqi¹,

Kazlauskas²

1995

Can. J. Chem.

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Sulfoxides are valuable chiral auxiliaries because they direct the formation of carbon~arbon bonds. As a route to enantiomerically pure sulfoxides, we examined hydrolase-catalyzed kinetic resolution by hydrolysis of apendant acetoxy group. Screening hydrolases for the enantioselective hydrolysis of the acetate in 2-(methylsulfiny1)phenyl acetate, lb, identified cholesterol esterase (CE) as the most enantioselective enzyme. The enantiomeric ratio, E, ranged from 10 to 25, favoring the (R) configuration at sulfur. Competing chemical hydrolysis of l b caused the large range in the measured values of E. A small-scale (250 mg) resolution of (2)-l b yielded (S)-lb with >99% ee (1 1 % yield) after recrystallization. Changing the methyl substituent to phenyl or n-butyl did not significantly change the enantioselectivity (E = 10 and 15, respectively), but changing it to a chloromethyl substituent lowered the enantioselectivity slightly (E = 5). Changing the phenyl acetate to a naphthyl acetate (2-(phenylsulfiny1)phenyl acetate vs. 1-(phenylsulfiny1)-2-naphthyl acetate) increased the enantioselectivity from 10 to 19. In all cases CE favored the (R)-sulfoxide. To aid the design of new resolutions with CE, we propose an empirical rule that accounts for the observed enantiopreference of CE toward these 5 sulfoxides and 15 other chiral aryl acetates. This empirical rule uses both the size of the substituents and their conformational preferences to predict which enantiomer reacts faster.Key words: kinetic resolution, lipase, cholesterol esterase, sulfoxides, empirical rule, Resume : Les sulfoxydes sont des auxiliaires chiraux utiles parce qu'ils orientent la formation de liaisons carbone-carbone. Dans le but d'obtenir des sulfoxydes Cnantiomeriquement purs, on a examine la possibilitC d'utiliser une rtsolution cinCtique catalysCe par une hydrolase impliquant l'hydrolyse d'un groupe acCtoxy. Une Cvaluation des hydrolases pour leur capacitt a effectuer l'hydrolyse CnantiosClective de llacCtate de 2-(mCthylsulfinyl)phCnyle, lb, a permis d'identifier 13estCrase de cholestCro1 (CE) comme l'enzyme le plus CnantiosClectif. Le rapport CnantiomCrique, E, vane de 10 a 25 et il favorise la configuration (R) au niveau du soufre. L'hydrolyse chimique compCtitive du composC l b provoque les grandes variations observkes dans les valeurs mesurCes de E. Une rCsolution preparative 5 faible Cchelle (250 mg) du composC (2)-lb conduit, aprks recristallisation, au (S)-lb avec un ee >99% (rendement de 11%). Lorsqu'on change le substituant de mCthyle 2 phCnyle ou n-butylC, il n'y a pas de changement significatif d'CnantiosClectivitC (E = 10 et 15, respectivement); toutefois, si on le remplace par un chloromCthyle, 1'CnantiosClectivitC est 1Cgkrement diminuCe (E = 5). Si l'on remplace I'acttate de phCnyle par 1'acCtate de naphtyle (acCtate de 2-(phCnylsulfiny1)phtnyle vs. acetate de 1-(phCnylsulfiny1)-2-naphtyle) 1'CnantiosClectivitC passe de 10 a 19. Dans tous les cas, la CE favorise le (R)-sulfoxyde. Dans le but d'aider au dtveloppement de...

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“…[4] Moreover, the kinetic resolution is also the main route for the preparation of axially chiral phosphine-based ligands. [5] Recently, a new method of dynamic kinetic resolution (DKR) of biaryl atropisomers, which occur in tandem, with in situ racemization and resolution, probably provides one of the most convenient and efficient approaches to a wide range of enantiomerically enriched axially chiral phosphine ligands. [6] Since Kagan found a bisphosphine ligand, DIOP, in 1972, [7] the development of chiral phosphine ligands has been concentrating on the design and preparation of bisphosphine compounds.…”

Section: Introductionmentioning

confidence: 99%

Asymmetric Synthesis of Chiral Atropisomeric Bis-Aryl Organophosphorus from Menthyl H-Phosphinate

Yang

2016

The Chemical Record

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This review describes new methods for the synthesis of chiral monophosphine ligands with menthyl phenylphosphinate as a chiral auxiliary through asymmetric Suzuki-Miyaura cross-coupling reactions and asymmetric C-H functionalization. The chiral menthyl phenylphosphinate as a chiral auxiliary is easy to prepare and the menthyl group can easily be transformed into other functional groups, with the chiral center synchronously remaining. These methodologies provide highly efficient and practical strategies for the synthesis of novel axially chiral biaryl monophosphine oxides and their corresponding phosphines. Meanwhile, these reactions are easy to handle and exhibit wide scope for substrates with excellent diastereomeric ratios.

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Kinetic Resolution of Phosphines and Phosphine Oxides with Phosphorus Stereocenters by Hydrolases

Cited by 38 publications

References 1 publication

Enzymatic Synthesis of Enantiopure Precursors of Chiral Bidentate and Tridentate Phosphorus Catalysts

Enzymatic Synthesis of Enantiopure Precursors of Chiral Bidentate and Tridentate Phosphorus Catalysts

Kinetic resolution of sulfoxides with pendant acetoxy groups using cholesterol esterase: substrate mapping and an empirical rule for chiral phenols

Asymmetric Synthesis of Chiral Atropisomeric Bis-Aryl Organophosphorus from Menthyl H-Phosphinate

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