The role of Pseudomonas cepacia lipase in the asymmetric synthesis of heterocyclic based compounds

Journal of Molecular Catalysis B: Enzymatic 122 (2015) 93–116

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Journal of Molecular Catalysis B: Enzymatic journal homepage: www.elsevier.com/locate/molcatb

The role of Pseudomonas cepacia lipase in the asymmetric synthesis of heterocyclic based compounds Ghodsi Mohammadi Ziarani a,∗ , Parisa Gholamzadeh a , Paria Asadiatouei a , Negar Lashgari b a b

Department of Chemistry, Alzahra University, Vanak Square, P.O. Box 1993893973, Tehran, Iran School of Chemistry, College of Science, University of Tehran, Tehran 14155-6455, Iran

a r t i c l e

i n f o

Article history: Received 12 May 2015 Received in revised form 27 August 2015 Accepted 30 August 2015 Available online 4 September 2015

a b s t r a c t Pseudomonas cepacia lipase (lipase PS) is an efficient enzyme which catalyzes the enantioselective asymmetric esterification and/or hydrolysis reactions in high yields and enantio excess of products. In this review, the role of lipase PS in the asymmetric esterification and hydrolysis of various heterocyclic compounds or their precursors is investigated. © 2015 Elsevier B.V. All rights reserved.

Keywords: Pseudomonas cepacia lipase Lipase PS Asymmetric synthesis Enantioselective reactions Enzyme

Contents 1. 2.

3.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93 1.1. Catalytic triad. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .94 Asymmetric synthesis of heterocycles using lipase PS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94 2.1. Esterification reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94 2.2. Hydrolysis of esters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115

1. Introduction Louis Pasteur is the first scientist who could separate two enantiomers of tartaric acid and said “The universe is chiral”. Many natural products are produced as chiral compounds. Asymmetric reactions produce optically active substances using one of the chiral substrates, catalysts, solvents and/or auxiliaries. In this regards, enzymes are important natural chiral catalysts [1].

Abbreviations: lipase A or ANL, Aspergillus niger lipase; CAL-A, Candida antarctica lipase A; CAL-B, Candida antarctica lipase B; CCL, Candida cylindracea lipase; CRL, Candida rogusa lipase; PPL, Pancreas porcine lipase; lipase PS or PCL, Pseudomonas cepacia lipase; lipase AK or PFL, Pseudomonas fluorescens lipase. ∗ Corresponding author. Fax: +98 2188041344. E-mail addresses: [email protected], [email protected] (G. Mohammadi Ziarani). http://dx.doi.org/10.1016/j.molcatb.2015.08.022 1381-1177/© 2015 Elsevier B.V. All rights reserved.

Lipase is an important enzyme which catalyzes the hydrolysis of lipids and has various applications and industrial potentials. Claude Bernard was the first who discovered lipases from pancreatic juice in 1856, and since then, animal pancreases have become the main source for the commercial lipases [2]. Many industrial applications of lipases are focused on its regio- and enantio-selectivity properties since they can catalyze asymmetric hydrolysis reactions at room temperature (save energy economically) and are active in both water and/or organic solvents [3]. Pseudomonas cepacia lipase or Pseudomonas sp. lipase or Burkholderia cepacia lipase summarized as PS or PCL is an efficient lipase in the transesterification of prochiral or racemic alcohols with acetates. It has been also Immobilized on different supports such as modified ceramic (PS-C), diatomite (PS-D) and Hyflo Super Cell (PS-HSC). In continuation of our experimental researches in asymmetric synthesis using lipases [4–8], this article aims to review

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the role of lipase PS in asymmetric esterification and/or hydrolysis of heterocyclic based compounds or their precursors. Its catalytic activity will be discussed in the next section. 1.1. Catalytic triad A catalytic triad refers to the three amino acid residues that function together at the center of the active site of certain hydrolase enzymes. Each amino acid plays a role as an acid, base or nucleophile in hydrolysis reactions, so they constitute an acid-basenucleophile triad catalytic center. The acidic residue is commonly aspartate (Asp) and/or glutamate (Glu). Although no natural amino acids are strongly basic, histidine (His) is an effective base since its pKa allows for base catalysis as well as hydrogen bonding to the acid residue using its imidazole moiety. Lysine (Lys) is another amino acid, which plays the role of a base. Although the 20 naturally occurring biological amino acids do not contain sufficiently nucleophilic functional groups, however the most commonly used nucleophiles are the alcohol group of serine (Ser) and the thiol group of cysteine (Cys). Ser–His–Asp, Ser–Glu–Asp and Cys–His–Asp are some examples of the classic triad-containing enzymes [9–16]. Lipase PS’s active site cleft is void and has 10 Å × 25 Å across. It has a catalytic triad of Ser87, His286 and Asp264 (Ser–His–Asp) which forms a number of hydrogen bonds [17]. The mechanism of transesterification in the presence of Ser–His–Asp triad of lipase PS is shown in Scheme 1. The hydroxyl group of serine acts as a nucleophile while histidine as a basic amino acid accepts the proton from the nucleophilic atom and then the nucleophilic attack occurs. Simultaneously, the carboxylic group of aspartic acid is hydrogen bonded with histidine and makes it more electronegative. When the hydroxyl group of serine attacks to the carbonyl of ester, histidine accepts its proton (part a). By joining of serine oxygen to the carbonyl group of an ester (part b), the R2 O− group is removed as an alcohol after moving off a histidine’s proton (part c). Chiral or prochiral alcohol, then attacks the carbonyl group of serine (part c) and serine-carbonyl bond is cleaved (part d). Finally, chiral ester is produced and the active cite switches back to produce more esters (part e) [18]. 2. Asymmetric synthesis of heterocycles using lipase PS In asymmetric syntheses, the selectivity of the reaction is determined by enantiomeric excess (ee.) and diastereomeric excess (de.), when the products are enantiomers and/or diastereomers, respectively. The enantioselectivity of a biocatalytic reaction is normally described by the enantiomeric excess (ee.) or the E value. In an enzymatic resolution of a racemic substrate, the E value can be calculated from Eq. (1) while the ee. value of the product is known. Where c is the conversion of substrate, and eep and ees are the obtained enantiomeric excesses of product (P) and remaining substrate (S), respectively. In order to provide both the product and the remaining substrate in high amount of ee. in one reaction step, the E-value should be high, usually around or more than 100 [19]. E=

ln[1 − c(1 + eep ) ln[1 − c(1 − eep )

1

2.1. Esterification reaction Formoterol 5, a highly ˇ2 -selective agonist [20], was synthesized from chiral epoxide 4 as shown in Scheme 2. For the preparation of epoxide 4, Campos et al. brominated and reduced ketone 1 to the corresponding bromoalcohol 2. Then, (S)-enantioselective esterification of racemic bromoalcohol 2 was accomplished using lipase PS and vinyl acetate. PPL was also used for this aim, but did

not lead to any products after 22 h. The pure (R)-bromoalcohol 2 and (S)-bromoacetate 3 were converted to (R)- and (S)-epoxides 4, respectively [21]. A synthetic route to 4-O-acetyl-l-rhodiopyranose 10 and 5-Oacetyl-l-rhodinofuranose 11 was described via a tandem Sharpless asymmetric dihydroxylation (AD) and lipase-catalyzed esterification (Scheme 3). In this method, alcohol 6 was oxidized to the corresponding aldehyde and went through the condensation with racemic 1,2-diphenyl-1,2-ethanediol (stilbene diol) to afford 7, which was then dihydroxylated by AD-mix-␣ [(DHQ)2 1 , EtOAc] to provide chiral diol 8. Esterification of diol 8 in the presence of PS lipase produced a separable mixture of acetates 9a and 9b, and minor amounts of diol 3. Hydrolysis of mono acetate 9a formed rhodiopyranose 10 and alternatively 9b was subjected to identical reduction reaction to gain rhodinofuranose 11. The trideoxyhexose l-rhodinose 10 and 11 are common constituents of many antibiotics, including rhodomycin, streptolydigin, vineomcyin B2 , and galtamycin [22–24]. Although, the final product of many synthetic routes towards trideoxyhexose l-rhodinose was isolated as an equilibrium mixture of pyranose 10 and furanose 11 [25], however, this lipase-catalyzed reaction gave the products separately. Ramadas and Krupadanam reported kinetic resolution (R)enantioselective acylation of (±)-dimethoxyethoxymethyloxy-2acetoxymethyl-2,3-dihydrobenzofuran 13 using lipase PS to give (R)-(−)-acetate 14 and (S)-(+)-13. Then, (R)-(−)-acetate 14 was hydrolyzed and in some steps converted to (R)-(−)-MEM-protected arthrographol 15 as a natural product [26]. (R)-(−)-arthrographol was reported to possess antifungal and chitin synthase inhibitor activity (Scheme 4) [27]. A family of enantiomerically pure benzofurans 19a–e was prepared by means of an asymmetric enzymatic process followed by an intramolecular chemical cyclization reaction (Scheme 5). Two lipases PS-C and CAL-B were used in this enzymatic reaction and PS-C showed an excellent selectivity toward alcohol 17a, achieving the best stereocontrol and allowed the recovery of the (R)-acetates 18a–e up to 99% ee in all cases. However, CAL-B showed lower stereopreference values [28]. Chenvert et al. reported the total synthesis of enterolactone 25 using lipase PS-catalyzed esterification of diol 21, prepared from reduction of diester 20. The lipase was (R)-selective with high enantio excess of the product. This synthesis was completed in 5 steps, including the hydroxyl group mesylation of compound 22, replacement of mesylate with cyanide, hydrolyzation of cyanide, ring closing, alkylation in 24 and finally deprotection to give enterolactone 25 as human lignin (Scheme 6) [5]. Esterification of 3-hydroxy-4-trityloxybutanenitrile 27 in the presence lipase PS-C resulted in the formation of (S)-alcohol 27 and (R)-acetate 28 in good yields and high enantioselectivities. The chiral products (S)-27 and (R)-28 has been utilized for the synthesis of enantiomerically pure 1,3-oxazolidine-2-ones (S)-29 and (R)-30 as a precursor for the synthesis of ␤-adrenergic blocking agents and oxazolidinone based antimicrobial agents, respectively (Scheme 7). Other lipases such as CRL, AK, CCL, CAL-B, PS-D and PS were also subjected to this reaction. The E values of all these lipases were more than 200, but PS-C had E = 1057 in the shorter period of time than the others [29]. Difluorinated analogue of (+)-eldanolide 34, a sex pheromone of male Eldana saccharina, was synthesized through the lipasecatalyzed reaction and intramolecular radical cyclization. (S)Enantioselective acylation of (±)-32 was achieved using lipase PS in the presence of excess amount of vinyl acetate and 2,6-di-t-butyl-4methylphenol (BHT) as the antioxidant in diisopropyl ether (DIPE)

1

Dihydroquinine.

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Scheme 1. The role of Ser–His–Asp triad of lipase PS in the transesterification reaction.

as solvent. Then, the pure optically active alcohols (R)- and (S)-32 were used for the synthesis of ␣,␣-difluoroeldanolide (4R,5R)-35 and its antipode (4S,5S)-35 (Scheme 8) [30]. ␤-Benzyl-␥-butyrolactones are the core framework of lignan structures [31]. The PS lipase-catalyzed esterification of the racemic ␥-hydroxy ester 36, coupled with subsequent acid-mediated cyclization, was an effective method to give both enantiomers of ␤-benzyl-␥-butyrolactone 38 (Scheme 9). This esterification enzymatic process was R-enantioselective and resulted in the products with high enantiomeric excess under mild reaction conditions [32]. A cupreous chafer beetle sex pheromone (R,Z)-(−)-5-(l-octenyl) oxacyclopentan-2-one 42 has been prepared employing lipase PS-catalyzed (R)-selective acylation of racemic 4-hydroxy-Sdodecynonitrile 40. Hydroxynitrile (±)-40 was prepared on a large scale from the alkylation of 3-formylpropionitrile 39 with (1octynyl)-magnesium bromide in THF. Then, the racemic mixture of 40 was subjected to lipase PS catalyzed acylation to yield (R)acyloxy nitrile 41 in 89% ee. Further enantiomeric enrichment was performed by repetition of the enzymatic reaction which yielded (R)-41 with over 99% ee. Then, it was hydrolyzed and subsequently hydrogenated to yield the natural pheromone (R,Z)-42 (Scheme 10) [33]. Takabe and coworkers found that lipase PS-catalyzed kinetic resolution of the N,N-diethyl-butanamide 43 gave the corresponding acetate 44 with (R) configuration. They hydrolyzed the acetate

and used chiral butanamide (S)-43 in cyclization reaction to give chiral butanolide 45 without racemization. (R)-Butanolide 45 was then effectively transformed into highly stereocontrolled virginiae butanolide C 46 as the precursor of factor-A (Scheme 11) [34]. Racemic 5-(hydroxy)-(5H)-furan-2-one 47 was reacted with vinyl acetate catalyzed by lipase PS-HSC to give (R)-selective ester enantiomer 48 and unreacted (S)-alcohol 47 (Scheme 12). In situ racemization of (−)-47 was spontaneously observed under the reaction condition and hence, conversion to (R)-48 was almost completed by coupling the kinetic resolution to an asymmetric transformation (second order asymmetric transformation) [35]. Various (R)- and (S)-l-trimethylsilyl-l-alkyn-3-ols 49 were synthesized by (R)-enantioselective acetylation in the presence of immobilized lipase PS. These chiral building units are useful key intermediates in the synthesis of biologically active compounds, e.g. prostaglandins [36]. The resolution can be applied to the synthesis of (R)- and (S)-5-octyl-2-(5H)-furanones 51 (Scheme 13) [37]. For the first time at 2004, Takabe and coworkers described the preparation of (18S)-variabilin 58 which is a natural product obtained from the sponge. Initially, lipase PS-catalyzed asymmetric desymmetrization of 1,3-propanediol 52 gave the mono-acetate (R)-53 which was reduced and converted into the (S)-sulfonyl silane 54. Subsequently, it was coupled with the furanyl side chain 56 to lead the substrate 57 in satisfactory yield. After desulfonylation, deprotection and TPAP-oxidation reaction in the presence of LDA

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Scheme 2. Synthesis of formoterol.

Scheme 3. Total synthesis of l-rhodinose compounds.

and tetronate, the reaction was followed by dehydroxylation under basic conditions and demethylation to obtain the target molecule (18S)-52 (Scheme 14). (18S)-Variabilin 58 can be also synthesized in another pathway as shown in Scheme 15. After subjecting of racemic diol 60 to transesterification by lipase PS, the (R)-product 61 was employed as a precursor for the synthesis of the target 58 [38]. Enantiomerically pure cis- and trans-2-substituted-3,6dihydro-2H-pyran-3-ols 62 have been prepared in the presence of an (R)-enantioselective lipase PS-C using vinyl acetate. The enantiopure products 62 and 63 can be readily reduced to give the corresponding optically active dihydropyrandiols 64 or

transformed into their 6-deoxysugar 65a–f counterparts using a traditional dihydroxylation protocol (Scheme 16) [39]. Racemic 3-aryl-2-nitropropanols 67a–e were prepared via the condensation reaction of nitromethane with aromatic aldehydes 66a–d, formalin and subsequent mediated reduction using baker’s yeast. The esterification reaction of these propanols 67a–e to give (S)-acetates 68a–e and (R)-alcohols 67a–e was investigated in the presence of lipase PS as the catalyst (Scheme 17). In addition, (R)-propanol 67e was converted to (R)-3-aminocroman 69e as a precursor moiety in the synthesis of Robalzotan, a selective antagonist of the 5-HT1A receptor [40].

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97

Scheme 4. Synthesis of (R)-(−)-MEM-protected arthrographol.

Scheme 5. Synthesis of benzofurans.

Scheme 6. Total synthesis of enterolactone.

5,6-Epoxyhexanoates 74 and 75 are efficient precursors for the synthesis of 6-substituted 6-lactone derivatives such as 76a–b [41]. As shown in Scheme 18, chiral 5,6-epoxyhexanoates 74 and 75 were achieved from (S)-73 which was prepared through asymmetric esterification of compound 71 in vinyl acetate using lipase PS as the catalyst. In this esterification reaction, lipase PS was (S)-

selective and resulted in quantitative chemical yields with high enantiomeric excesses (98% ee.) [42]. The efficient resolution of various ␣-alkyl-␣-hydroxymethyl cyclopentanones 77 was generated by lipase PS or AK-catalyze esterification with vinyl acetate as the acyl donor in pentane or benzene. Amano PS was very efficient to resolve the ␣methyl-substituted ␤-ketoalcohols 77a–b and was (R)-selective to

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Scheme 7. Synthesis of enantiomerically pure 1,3-oxazolidine-2-ones.

O O

OH

(4S,5R)-34 (91% ee.) (+)-Eldanolide or F F

(R)-32 (63%, 91% ee.)

O 31

n-BuLi, THF

OH

lipase PS (4R,5R)-35 (>99% ee.)

CH2 =CHOAc BHT, DIPE

-78-0 °C, 9 h

O O

32 OAc

(S)-33 (28%, 98% ee.) F OH

F O

O (S)-32

(4S,5S)-35 (98% ee.)

Scheme 8. Synthesis of difluorinated analogue of (+)-eldanolide.

Scheme 9. Synthesis of both enantiomers of ␤-benzyl-␥-butyrolactone.

acetylation. On the contrary, Amano PS was not an efficient catalyst for the acylation of 77c–e; hence, Amano AK was used and gave a good resolution in benzene. The obtained enantiopure alcohols 77a–e were used as the precursors in the synthesis of optically active pseudo-iridolacetones 79a–e (Scheme 19) [43].

The coupling reaction between phenol derivatives 80a–b and 4-penten-2-ol 81 was done in the presence of diisopropyl azidocarboxylate (DIAD) to gain 82a–b. The reaction was then followed to give 83a–b which were separately reacted with lipase PS for highly (S)-enantioselstive esterification reactions. After the separation of compounds 83 and 84, (S)-83a and b resulted in the

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Scheme 10. Synthesis of beetle sex pheromone.

Scheme 11. Synthesis of butanolide.

Scheme 12. (R)-selective esterification of racemic 5-(hydroxy)-(5H)-furan-2-one.

Scheme 13. Synthesis of (R)- and (S)-5-octyl-2-(5H)-furanones.

formation of 4-chromanones 85a–b by intramolecular cyclization reaction (Scheme 20) [44]. 2-Phenylchroman-4-one 88 was synthesized in its optically active form via lipase PS-catalyzed (R)-enantioselective esterification reaction of (±)-86 with vinyl acetate in isooctane (Scheme 21). Compound (S)-86 was converted into (R)-88 after three steps, while compound (R)-7 was hydrolyzed, treated with lipase PS, and rehy-

drolyzed to result in (R)-86 with over 99% ee, which was then converted to (S)-88 [45]. The 2-substituted chroman-4-one skeleton can be found in many natural products with various biological activities such as anthelmintic and plant growth inhibition activities [46–49]. Synthesis of (R)-enantiomers of 4-chromanone such as ␣tetralone and ␣-indanone scaffolds 91 was reported from

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Scheme 14. Synthesis of (18S)-variabilin.

Scheme 15. Synthesis of (18S)-(−)-variabilin.

(R)-alcohols 89. Lipase PS esterification reaction of a racemic mixture of compounds 89 gave (R) -acetates 90 in high enantioselectivity which were then hydrolyzed to yield (R)-alcohol 89 (Scheme 22). Other lipases such as AK, A, F, PS-D, CAL-B, and Lipozyme were also tested in this reaction, but their E values did not exceed than 57; however, it was more than 154 for lipase PS [50]. The sulfone 94 was prepared from the monoacetate product 93 of the lipase PS-catalyzed acetylation of anti,anti-2,4-dimethyl1,3,5-pentantriol (meso-92). Then, the sulfone 94 was converted to stigmatellin 96, which is a natural antibiotic, in several steps (Scheme 23) [51]. Melais and coworkers reported the PS lipase-catalyzed resolution of heteroaromatic secondary alcohol 97 with succinic anhydride 98 under different conditions including microwave (MW) radiation and ultrasonication (US) [52]. (R)-4-chromanol 97 was obtained in optically pure form (ee > 99%) with a high selectivity E > 200 in Et2 O in the presence of lipase PS, using MW and/or US. The reaction time was reduced compared to the conventional heating with a better control of the selectivity of the lipase PS (Scheme 24). Acetylation of primary alcoholic group (C-22) of silychristin 100 was performed by lipase PS-D using vinyl acetate as an acetyl donor, whereas the selective deacetylation of 22-O-acetyl silychristin 101 was accomplished by CAL-B in methyl tert-butyl ether/n-butanol. Both of these reactions occurred without diastereomeric discrimination of silychristin (Scheme 25) [53]. Serra and Lissoni reported the first enantioselective synthesis of ambliol-A 106 [54]. Ambiol-A 106 is a major metabolite of marine sponge Dysidea amblia. The synthesis was started from racemic ␣ionone 102. The key step of the synthesis was PS lipase-mediated resolution of 4-hydroxy-␥-ionone 103. The obtained acetate enantiomer 104 was converted to trans-␣-epoxy-dihydroionone 105 which is the precursor of ambiol-A 106 synthesis (Scheme 26).

Bracher and Papke employed lipase PS as the catalyst in the esterification reaction of racemic 2-methyl-3-(2-thiophene)-1propanol 107 to give (R)-alcohol 107 together with (S)-ester 108. The latter was then converted to the racemic alcohol 107 using saponification reaction followed by racemization via sodium and benzophenone in toluene (Scheme 27). It is worthy to note that thiophene ring is stable under this racemization condition [55]. Duloxetine 112 is a serotonin-norepinephrine reuptake inhibitor for treatment of major depressive disorder, marketed as (S)-enantiomer [56]. A simple and highly enantioselective synthesis of (S)-duloxetine 112 has been accomplished by employing lipase PS-D in the esterification reaction of 3-hydroxy-3-(2thienyl) propanenitrile 110 (Scheme 28). Other lipases such as Lipozyme, CRL, CCL, and PPL were investigated in this reaction and did not have good results as well as lipase PS-D [57]. In a study by Kamal et al., The resumes -azidoalcohols 114a–b were prepared in a three step process: Friedel–Crafts acylation, azide nucleophilic displacement, and final reduction. -Azidoalcohols 114a–b, the precursor of -aminoalcohols, were then treated with lipase PS-D and alcohols (S)-114a and (S)-114b were obtained in high enantiopurity (99% and 95% ee., respectively) together with the corresponding acetates (R)-115a and (R)-115b. The deacetylation reaction of acetates gave (R)-alcohols 114a–b with retention of configuration and enantiopurity and compounds (S)-114a–b were reduced and converted into the corresponding (S)-116 and (S)-duloxetine 112 (Scheme 29). It is worth mentioning here that (S)-enantiomer of the duloxetine is more biologically active than the R-enantiomer [58]. 2-t-Butoxycarbonylamino-2-methyl-1,3-propanediol 117 was selected as a substrate in the synthesis of (S)-N-Boc-N,O-isopropylidene-␣-methylserinal 119 and (4R)methyl-4-[2-(thiophen-2-yl) ethyl]oxazolidin-2-one 120. For this aim, lipase PS catalyzed esterification reaction of diol 117

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Scheme 16. Synthesis of dihydropyrandiols and their 6-deoxysugars.

Scheme 17. Synthesis of (R)-3-aminocroman.

101

102

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Scheme 18. Synthesis of 5,6-epoxyhexanoates and 6-substituted 6-lactone derivatives.

Scheme 19. Synthesis of pseudo-iridolacetones.

Scheme 20. Synthesis of 4-chromanones.

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Scheme 21. Synthesis of 2-phenylchroman-4-one.

Scheme 22. Synthesis of ␣-tetralone and ␣-indanone scaffolds.

Scheme 23. Synthesis of stigmatellin.

Scheme 24. Kinetic resolution chroman-4-ol.

103

104

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Scheme 25. Selective acetylation of primary alcoholic group (C-22) of silychristin and deacetylation of 22-O-acetyl silychristin.

Scheme 26. Enantioselective synthesis of ambliol-A 106.

Scheme 27. Kinetic resolution of of racemic 2-methyl-3-(2-thiophene)-1-propanol.

Scheme 28. Synthesis of duloxetine.

was developed and (R)-monoacetate was obtained to use in the synthetic process of compounds 119 and 120 (Scheme 30) [59]. Racemic azirine (±)-122 was prepared from cinnamyl alcohol 121. Then, in the presence of lipase PS, it gave (S)-(+)-phenyl-2Hazirine-2-methanol 122 and the corresponding acetate (R)-(−)-123

at −40 ◦ C in ether and under unusual conditions for enzyme (Scheme 31) [60]. The ␤-lactam ring is not only the core structure of several antibiotics [61], but also it can undergo ring-opening to give valuable ␤-amino acids [62]. The racemic ␤-lactams 125a–b, pre-

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105

Scheme 29. Synthesis of both enantiomers of duloxetine.

Scheme 30. Synthetic process of (S)-N-Boc-N,O-isopropylidene-␣-methylserinal 119 and (4R)-methyl-4-[2-(thiophen-2-yl) ethyl]oxazolidin-2-one 120.

Scheme 31. Kinetic resolution of azirine.

Scheme 32. Enantiopure preparation of ␤-lactams.

pared from styrene 124a or 4-methylstyrene 124b, were subjected to lipase PS catalyzed asymmetric (R)-selective butyrylation to prepare enantiopure 4-aryl-2-azetidinones (S)-125a–b and (R)126a–b. Butyrylation reaction resulted in high selectivity rates in the case of phenyl-substituted compounds, while the 4-(p-tolyl) derivatives reacted with much lower selectivities (Scheme 32).

Other lipases such as lipase AK and PPL were also used in this study for asymmetric butyrylation of (±)-125a–b and acceptable results were obtained while CAL-A (lipase from Candida antarctica A) was insufficiently selective [63,64]. Fülöp and coworkers used derivatives of such chiral ß-lactams for the synthesis of optically

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Scheme 33. An enzymatic procedure for the synthesis of taxol precursor.

Scheme 34. Kinetic resolution of imidazole.

Scheme 35. Enantiopure synthesis of imidazolium ionic liquids.

active diaminocarboxylates and 1-aminoindane-2-carboxylic acid cispentacin benzologue [65,66]. A similar enzymatic strategy was used for the preparation of a key intermediate for the taxol 131 side-chain from N-hydroxymethylated cis-3-acetoxy-4-phenylazetidin-2-one 128. Lipase PS catalyzed acylation of the primary OH group using vinyl butyrate furnished the corresponding diester 129 and unreacted monoester 128 with excellent enantiomeric excess values (ee ≥ 98%). Finally, the diester enantiomer 129 was hydrolyzed through acidic condition to give the key intermediate of taxol 131 (Scheme 33) [67]. Ema et al. used an enzymatic method for the determination of absolute configurations. In this study, the esterification reaction of racemic alcohol 132 in the presence of (R)-enantioselective lipase PS as one of the alcohols tested in the esterification reaction, in the presence of (R)-enantioselective lipase PS, resulted in the forma-

tion of (R)-acetate 133 (Scheme 34) [68]. Then, the results were compared with the Mosher’s method (MTPA) [69] and it was concluded that enzymatic method is a rapid, easy, economical, and reliable method in comparison with MTPA method, at least for 1-substituted ethanols [68]. Busto et al. synthesized enantiopure imidazolium ionic liquids 138 and 139 at room temperature. These ionic liquids were prepared by R-selective lipase PS-C-catalyzed esterification reaction of alcohol 136 which was prepared by the reaction of epoxide 134 and imidazole 135 (Scheme 35). CAL-B was also tested in this reaction and good yields of products were obtained, but the reactions required 39 h for completion [70]. In another publication, a series of racemic trans-1,2,3,4tetrahydronaphthalen-2-ols 141 has been synthesized by ring opening reactions of epoxide 140a–b using imidazole or 1,2,4triazole. The kinetic resolutions of these racemate compounds were

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Scheme 36. Resolution of trans-1,2,3,4-tetrahydronaphthalen-2-ols.

Scheme 37. Synthesis of pyrrolidine.

Scheme 38. Synthesis of chiral 5-hydroxypyrrolidin-2-ones.

Scheme 39. Synthesis of (−)-2-epi-lentiginosine and (S)-nebracetam.

accomplished by the use of lipase PS-C through a transesterification processes which the products were obtained with high to excellent enantiodiscrimination values (Scheme 36) [71]. Trans-2,5-bis(hydroxymethyl) pyrrolidine is a practical chiral auxiliary in asymmetric reactions [72,73]. Sibi and Lu reported the synthesis of pyrrolidine 144 and the effect of lipase PS on the enantioselective acetylation of this compound. It was observed that di-acetylation reaction was R-selective while mono-acetylation was S-selective in the mixture of hexane and dichloromethane as solvents (Scheme 37). Furthermore, using THF or dichloromethane as solvents, mono-acetylation was R-selective, but the yield of diacetate became lower than 20% [74]. Succinimide derivatives 147 were used in the synthesis of chiral 5-hydroxypyrrolidin-2-ones 148 that are important building blocks for the synthesis of natural products [75]. The reaction of 1,2dialkyl-5-hydroxypyrrolidin-2-one derivatives 148 in the presence

of lipase PS gave both (R)-acetate 149 and recovered (S)-alcohol 148 with high enantioselectivity (Scheme 38) [76]. The Lipase PS-D-catalyzed kinetic resolution of hydroxylactam 148 was performed by isolation–racemization of the chiral acetoxylactam (R)-151 to provide the optically pure hydroxylactam (S)-148, a chiral building block for alkaloids syntheses. Muramatsu and co-workers synthesized (−)-2-epi-lentiginosine 152 as a glycosidase inhibitor using (S)-hydroxylactam 148 in 10 steps in 20% total yield with no loss of enantiomeric excess (Scheme 39) [77]. In another report, (S)-148 was used in the synthesis of (S)-nebracetam 153a as a partial agonist presynaptically at muscarinic receptors [78]. Also, (S)-hydroxylactam 148 has been used as a precursor for the synthesis of AI-77-B natural compound [79], (+) and (−)Calyculin antipodes [80], and 3,4-dihydroxyglutamic acids [81]. Crispine A 156 is an isolated alkaloid from Carduus crispus, a Chinese plant which was used for the treatment of cold and rheumatism [82]. A total synthesis of crispine A 156 enantiomers

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Scheme 40. Total synthesis of Crispine A.

Scheme 41. Synthesis of chiral alcohol.

Scheme 42. Enantio-selective synthesis of epoxides.

has been developed via lipase-catalyzed acylation of the primary hydroxyl group of compound 154. The (S)-selective acylation of 154 occurred in two steps with vinyl decanoate using lipase PS

in t-BuOMe. Then, the ester enantiomer (S)-155 was hydrolyzed in K2 CO3 /MeOH to form the corresponding alcohols 154, which this condition was useful for a direct ring-closing reaction with-

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Scheme 43. Synthesis of non-narcotic analgesic.

Scheme 44. Kinetic resolution of Mannich product.

Scheme 45. Esterification reaction of pyrimidine nucleoside.

Scheme 46. Synthesis of vasicinone.

Scheme 47. Lipase esterification reaction of 3,3 -bis(hydroxymethyl)-2,2’-bipyridine-N,N-dioxide.

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Scheme 48. (−)-Deoxynupharidine synthetic path.

Scheme 49. Kinetic resolution of porphyrin.

Scheme 50. Asymmetric synthesis of methyl bacteriopheophorbide-d.

Scheme 51. Synthesis of 1,4:3,6-Dianhydro-D-glucitol 2-acetate and its isomeric structure.

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Scheme 52. Enantio-selective hydrolysis of ␥-azidoesters.

Scheme 53. Synthesis of both enantiomers of N-benzyl-3-hydroxypyrrolidine.

Scheme 54. Synthesis of indanoxazilidinone.

out deprotection and converted them to the desired (S)-156 (Scheme 40) [83]. Among the tested lipases, CAL-A, AK, CRL, and PPL did not catalyze the reaction. Acylation was very fast with CAL-B and PS-IM (immobilized lipase PS) but no and low enantioselectivity was observed, respectively. In this esterification reaction, lipase PS was (S)-selective with high enantiomeric excesses (94% ee.). Enantiopure alcohols (R)-, (S)-158 and (R)-, (S)-161 were prepared via enantioselective acylation in organic media, catalyzed by a lipase PS with high ee. >97% (Schemes 41 and 42). This lipasecatalyzed acylation reaction was (R)-enantioselective for alcohol 158 and (S)-enantioselective for alcohol 164. Then, each alcohol (R), (S)-161 which were converted to their epoxides (R)-, (S)-163, were reacted with deprotected piperidine (R)- or (S)-164 to give the final products 165. Hence, four stereoisomers of the non-narcotic analgesic 1-[2-(4-fluorophenyl)-2-hydroxyethyl]-4-[(4-fluorophenyl) hydroxylmethyl]-piperidine 165 were synthesized from chiral precursors 163 and 164 (Scheme 43) [84]. Racemate cis-2-(1-piperidinylmethyl) cyclohexanol 170 was prepared using Mannich reaction of cyclohexanone 167, formalin 168, and piperidine 171 followed by reduction by NaBH4 . The (R)enantioselective esterification of the racemic cyclohexanol 170 led to acetate (R)-171 and alcohol (S)-170 in the presence of PS lipase as the catalyst and vinyl acetate (Scheme 44) [85]. Acylonucleosides have various biological activities and are valuable in cancer therapy [86]. Lipase PS was used in the esterification reaction of pyrimidine nucleoside 172 and had selectivity towards

(R)-monoesters 173a–d with high enantiomeric purity in t-butyl methyl ether (TBME) as solvent (81–99% ee). The best selectivity was obtained from the esterification reaction with vinyl benzoate as the acylating agent (monoester 173c). The hydrolysis of prochiral diesters 174a–b, formed during the esterification reaction, in the presence of lipase PS provided the (S)-monoester as an opposite enantiomer (Scheme 45). CAL-B was another lipase that was also tested for this reaction, but it was unsuccessful in giving a selective acylation of enantiotopic hydroxyl groups [87]. Vasicinone 177 is an alkaloid extracted from the leaves of Adhatoda vasica [88,89]. A facile synthetic route for the formation of vasicinone 177 was developed by Kamal and co-workers using azidoreductive cyclization strategy employing TMSCl-NaI and bakers’ yeast. Resolution of vasicinone 177 has been carried out by employing lipase PS in the presence of vinyl acetate (Scheme 46). The enantiomeric ratio of (S)-vasicinone 177 to (R)-acetate 176 was 96:4 [90]. Chiral 2,2 -bipyridines (bipys) are valuable ligands in the field of stereoselective organic synthesis and transition metal catalysis [91]. Sanfilippo et al. used (±)-3,3 -bis(hydroxymethyl)2,2 -bipyridine-N,N-dioxide 178 in the lipase esterification to give pure enantiomers with axial chirality. Lipozyme and PS-D lipase were the lipases used in this reaction. Lipozyme was found to give good enantioselectivity; although, PS-D had low enantioselectivity and gave opposite stereopreference (Scheme 47) [92].

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Scheme 55. Synthesis and hydrolysis of ␤-heteroaryl-␤-amino esters.

Scheme 56. Synthesis of optically active epoxy alcohol.

Scheme 57. Enzymatic hydrolysis of 6-acetyloxy-2H-pyran-3(6H)-one.

Scheme 58. Enzymatic hydrolysis of crown and azacrown ethers.

The Nuphar alkaloids are a group of piperidine alkaloids isolated from Nuphar water lilies [93]. (−)-Deoxynupharidine 185 is one of the Nuphar alkaloids which was synthesized by Bates and coworkers. Significant step for this synthesis include the optimized enzymatic resolution of allenic ester 182 which was prepared from propargyl alcohol 181. Then, (S)-allenic alcohol 184 was converted to diene intermediate 184. The key intermediate 184 was converted to (−)-Deoxynupharidine 185 through an intramolecular reductive amination, saponification of the ester and cyclisation (Scheme 48) [94]. Large secondary alcohols, 5-[4-(1-hydroxyethyl) phenyl]10,15,20-triphenylporphyrins 186 designed on the basis of the transition-state model (Fig. 1), were subjected to the lipasecatalyzed esterification reactions. Based on the results and transition-state model, lipase PS was R-enantioselective and gave acetate (R)-187 (Scheme 49). Although, Chirazyme L-2, Chirazyme

L-9, and lipase LIP were also used in this reaction, the best result with high E values (>298) was obtained with lipase PS [95]. Naturally bacteriochlorophyll-ds are one of the major photosynthetic pigments that occur in various phototrophic bacteria [96,97]. Tamiaki et al. reported the asymmetric synthesis of methyl bacteriopheophorbide-d 188 by stereoselective borane-reduction of the acetyl group with chiral oxazaborolidines. Kinetic resolution esterification of 188 was then catalyzed by Amano PS lipase in toluene with vinyl acetate to give the corresponding acetate (3 R)-189 (Scheme 50) which was converted into (3’R)-188 by methanolysis in the presence of K2 CO3 . Toyobo, CCL, PPL, CAL, and PLE were other lipases tested in this reaction; in which Toyobo was the only one that showed the results close to PS lipase, and other lipases had no better activity. E-values for esterification reaction were 2.9 and 2.0 as catalyzed by Toyobo lipase and Amano PS, respectively. These low values are the result of the large size of

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Scheme 59. Synthesis of LTD4 (leukotriene D4 ) antagonists.

Scheme 60. Resolution of ␤-substituted ␥-((acetyloxy)methyl)-␥-butyrolactones.

Scheme 61. Resolution of dihydrofuranone.

the chlorin moiety and/or the steric hindrance around the hydroxyl group to bind into the active site of the enzyme [98]. 2.2. Hydrolysis of esters 1,4:3,6-Dianhydro-D-glucitol 2-acetate 192 and its isomeric structure 193 have been synthesized in the presence of lipase PS via acylation and deacylation reactions, respectively (Scheme 51). These products are two important precursors for the synthesis of nitrate esters which have therapeutic uses [99]. As mentioned before (Scheme 25), lipase PS has been used as a catalyst in the esterification reaction of ␥-azidoalcohols 114a–b.

Here, ␥-azidoalcohols 114a–b were esterified using acetic anhydride and then hydrolyzed by lipase PS to give the corresponding (R)-alcohols 114a–b and (S)-esters 115a–b (Scheme 52). Lipases PS, PS-D, PS-C, AK, and CAL were tested for the hydrolysis reaction and PS-C showed the best results, however, the E value for 114a and 114b was 147 and 15, respectively. The obtained E value for 114a is very good [58]. The synthesis of both enantiomers of N-benzyl-3hydroxypyrrolidine 195a and N-benzyl-3-hydroxypiperidines 195b–c were accomplished via enzymatic kinetic resolution of the corresponding racemic esters 194a–c (Scheme 53). Various commercially available hydrolases were studied in which the best

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Scheme 62. Synthesis of (S)-5-(hydroxymethyl)-4-alkylfuran-2(5H)-one.

Fig. 1. Transition-state model for enantioselective acetylation of porphyrin 186 using lipase PS [95].

results were obtained with lipases PS, AK, CAL-B and with protease Alcalase. Lipase and protease showed opposite enantiopreference on the esters, allowing the preparation of both enantiomers of the target compounds [100]. (4R,5S)-Indanoxazilidinone 198 and its enantiomer (4S,5R)-198 have been synthesized using selective hydrolyzation of racemic ester 196 in the presence of lipase PS (Scheme 54). CAL was also tested in this reaction, but the results was not useful. It is worth mentioning that chiral indanoxazilidinones are important chiral auxiliaries in asymmetric reactions [101]. ␤-Heteroaryl-␤-amino esters 200a–g can be synthesized starting from the nitrile compounds 199 and/or aldehydes in some steps (Scheme 55). The racemic amino esters 200a–b were then hydrolyzed to give the corresponding (R)-␤-amino esters 200a–g and (S)-␤-amino acids 201aa–g. Among the PPL, AK, and PS lipases, which have been used for this hydrolysis, PS lipase showed the best results with high E value (>200) [102]. Optically active epoxy alcohol (R)-204 is a chiral building block in the synthesis of enantiomerically pure natural products. This compound was prepared from the esterification reaction of diol 202 followed by epoxidation of the C C bond. Subsequent hydrolyzation of diester 203 was accomplished using lipase PS to give

(R)-epoxy alcohol (Scheme 56). Other enzymes such as PPL, M, FAPI5, WG, and Toyobo-LIP were (R)-selective, whereas CCL, acylase, and CRL were (S)-selective. Lipase PS was the only one that resulted in good yields (91%) with an enantiomeric excess of 79% in shorter reaction time. The use of PS together with THF as solvent, improved the enantiomeric excess of the product up to 99% [103]. Racemic 6-acetyloxy-2H-pyran-3(6H)-one 205 was resulated into its racemate alcohol 206 and (R)-acetate 205 (Scheme 57) in the presence of various lipases including PS, PS-HSC, AKG, and CAL. Despite the low E values resulted from these lipases, the best E value (16) in shorter reaction time was obtained by PS-HSC and lipase CCL gave the opposite enantiomer of ester (S)-205 in good E value (>35) [104]. It is noteworthy to mention that chiral pyranones are attractive synthons in the synthesis of natural products because of their multifunctional nature [105]. As shown in Scheme 58, lipase PS has been applied in the hydrolysis of ester substrate 207 which has crown ether and azacrown ether in its structure. Lipase PS has been observed as the most efficient catalyst in the presence of alkali metal salts, specially NaCl, which is related to non-covalent crown-metal interactions resulted in enhancement in enantioselectivity [106]. Selective hydrolysis of prochiral and racemic dithioacetal esters 209a–c has been performed in the presence of lipases PS to prepare (R)-210a–c. Diacids 210a–c and unreacted diesters 210a–c are the byproducts of this reaction which the lower amounts of them were obtained in the presence of lipase PS as the catalyst, especially when n = 1, high yield and ee of (R)-211b was obtained. Then, as shown in Scheme 59, the chiral compound (R)-211a was used in the synthesis of LTD4 (leukotriene D4 ) antagonists (R)-212a and (S)-212b which are used to treat some inflammation in asthma and allergic rhinitis by inhibiting the production or activity of leukotrienes [107]. Ha et al.reported the resolution of the synthetically valuable ␤substituted ␥-((acetyloxy) methyl)--butyrolactones 213a–b and 215a-–c to give their optically active forms using lipase PS as an efficient catalyst (Schemes 60–62) [108].

3. Conclusion During the Asymmetric reactions, optically active substances are produced using one of the chiral substrates, catalyst, solvent and/or auxiliary. Lipase is an important chiral enzyme which naturally catalyzes the hydrolysis of lipids. In addition, it has been used as an effective and green catalyst in many chemical syntheses which acts at room temperature and results in saving energy. This review gave an overview of the advances in the use of lipase PS in esterification and hydrolysis reactions to give optically active alco-

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hols and esters in good to high E values which led to enantiopure heterocycles.

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