A green route to enantioenriched (S)-arylalkyl carbinols by deracemization via combined lipase alkaline-hydrolysis/Mitsunobu esterification

Houiene, Zahia; Merabet‐Khelassi, Mounia; Bouzemi, Nassima; Riant, Olivier; Aribi‐Zouioueche, Louisa

doi:10.1016/j.tetasy.2013.01.020

Cited by 19 publications

(8 citation statements)

References 49 publications

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“…Both the inversion efficiency and yield depended on the aromatic substituents [36]. Recently, we observed almost full racemization during the nucleophilic substitution reaction due to the presence of an electron donating substituent ring [37].…”

Section: Deracemization By Combined Enzymatic Hydrolysis/mitsunobu Stmentioning

confidence: 96%

Enantiocomplementary Preparation of (S)- and (R)-Arylalkylcarbinols by Lipase-Catalysed Resolution and Mitsunobu Inversion: Impact of Lipase Amount

et al. 2014

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A series of arylalkylcarbinol derivatives were deracemized through sequential combination of Candida antarctica lipase B (CAL-B) catalyzed resolution by hydrolysis and Mitsunobu stereoinversion. The (S)-acetates were obtained in 71%-99% ee and 76%-89% yields. An enantiocomplementarity was established for the hydrolysis and acylation reactions with CAL-B lipase. Thus, the (S) and (R) enantiomers of Indan-1-yl acetate, 1,2,3,4-tetrahydro-1-naphthalenol acetate and 1-(2-naphthyl) ethyl acetate were obtained in 91%-99% ee and 76%-89% yield.

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Section: Deracemization By Combined Enzymatic Hydrolysis/mitsunobu Stmentioning

confidence: 96%

Enantiocomplementary Preparation of (S)- and (R)-Arylalkylcarbinols by Lipase-Catalysed Resolution and Mitsunobu Inversion: Impact of Lipase Amount

et al. 2014

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“…In another example, secondary benzylic acetates were deracemized employing a two-step protocol consisting of a CAL-B-catalyzed hydrolysis followed by a Mitsunobu reaction obtaining the (S)-acetates in high yields (70-89%) and moderate to excellent ee (57-99%). [133] Scheme 24. Preparation of (S)-15, key intermediate of (S)-coniine, via lipase-catalyzed hydrolysis plus Mitsunobu inverting protocol.…”

Section: Scheme 22mentioning

confidence: 99%

Why Leave a Job Half Done? Recent Progress in Enzymatic Deracemizations

Díaz‐Rodríguez¹,

Lavandera

Gotor³

2015

CGC

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Abstract. In recent years the usefulness of enzymatic systems to obtain a single stereoisomerically pure compound starting from a racemate has been expanded. Moreover, current advances in protein engineering, molecular biology and modeling tools are the basis to improve the catalytic properties of enzymes to face novel synthetic challenges. Also, medium engineering and novel immobilization methods of (bio)catalysts are enhancing the productivity of biocatalytic processes making them suitable for being scalable. The development of multienzymatic protocols and the combination of enzymes with other catalysts are providing a wide range of synthetic possibilities that are expanding the scope of these transformations even at industrial scale. Herein we will describe an overview of recent (chemo)enzymatic deracemizations, focusing on the strategy employed (dynamic kinetic resolution, stereoinversion, cyclic deracemization or enantioconvergent process), the type of substrate (e.g., alcohols, amines, carboxylic acid derivatives or carbonylic compounds), and the biocatalyst(s) used.

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“…The main objective of this process was to circumvent some of disadvantages of the conventional methods for enzymatic hydrolysis, such as the perturbation on the lipase's enantioselectivity due to the co-solvent nature as well as the difficulty of controlling the pH value of the aqueous solution during the hydrolysis procedure. The application of these alkaline hydrolysis by means of CAL-B and sodium carbonate in organic media gave an excellent resolutions which have been successfully applied to the deracemization process [20]. Moreover, this procedure has been successfully applied to deacylate numerous substrates with a high stereoselectivity such the chemoselective deacylation of N,O-protected amino alcohols [21], the enantio-and the diastereoselective deacylation of cis/trans -2-aryl-1-cyclohexanol derivatives [22] (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Two Approaches for CAL-B-Catalyzed Enantioselective Deacylation of a Set of α-Phenyl Ethyl Esters: Organic Solvent with Sodium Carbonate and Micro-aqueous Medium

et al. 2021

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Herein, we report an efficient enantioselective cleavage of the acyl-moiety of a set of α-phenyl ethyl esters with different chain-lengths catalyzed by lipase B from Candida antarctica (CAL-B) by comparing two reactional approaches: anhydrous media with sodium carbonates and micro-aqueous medium. The deacylation is performed in organic solvent, in the presence of Na2CO3 in the first case, and by addition of a drop of phosphate buffer solution pH=7 in the second. The results show the high efficiency of the deacylation in the presence of the sodium carbonate for the enzymatic resolution of all the esters and that in term of reactivity (31% ≤ conv ≤ 50%) and selectivity (E >200). While, during the hydrolysis in micro-aqueous media, the conversion is strongly affected by the length of the acyl-chain side, the conversion decreases from conv =50% with the 1-phenylethyl acetate 1a to conv =19% with 1-phenyethyl dodecanoate 6a, and this, even if the selectivity remains high (E>89). In both conditions, the lipase CAL-B shows a high enantioselectivities in favor of (R)-1-phenyl ethanol enantiomer (conv >45%, E>200) but the reactivity is modulated by the form and the size of the acyl-chain side.

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A green route to enantioenriched (S)-arylalkyl carbinols by deracemization via combined lipase alkaline-hydrolysis/Mitsunobu esterification

Cited by 19 publications

References 49 publications

Enantiocomplementary Preparation of (S)- and (R)-Arylalkylcarbinols by Lipase-Catalysed Resolution and Mitsunobu Inversion: Impact of Lipase Amount

Enantiocomplementary Preparation of (S)- and (R)-Arylalkylcarbinols by Lipase-Catalysed Resolution and Mitsunobu Inversion: Impact of Lipase Amount

Why Leave a Job Half Done? Recent Progress in Enzymatic Deracemizations

Two Approaches for CAL-B-Catalyzed Enantioselective Deacylation of a Set of α-Phenyl Ethyl Esters: Organic Solvent with Sodium Carbonate and Micro-aqueous Medium

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