The effect of vinyl esters on the enantioselectivity of the lipase-catalysed transesterification of alcohols

Kawasaki, Masashi; Goto, Michimasa; Kawabata, Sueo; Kometani, Tadashi

doi:10.1016/s0957-4166(01)00083-0

Cited by 62 publications

(30 citation statements)

References 36 publications

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“…For substrate 1, the best results (E = 3.6) were obtained with lipase Chirazyme Ò L-10 (entry 3) which is somewhat higher than obtained by others in a similar reaction. 15 This lipase seems to show an enantioselectivity of the same magnitude for three of the alcohols tested 1, 2 (entry 6, E = 4.1) and 4, (entry 14, E = 3.4) independent of the alkyl group at the stereogenic centre. Interestingly, when Chirazyme Ò L-10 was used with substrate 3, an unexpectedly high E-value value of 11.3 (entry 9) was obtained with the (+)-enantiomer reacting faster.…”

Section: Resultsmentioning

confidence: 84%

“…12,13 Very few examples are known from the literature when primary alcohols, with even more remotely located stereogenic centres, are resolved by enzymes in acylation reactions. 7,[14][15][16][17][18] Pseudomonas cepacia lipase (PCL) catalyzed resolution of (±)-3-phenyl-1-butanol 1 has been reported 15 with a very low E-value of 2 but the enantioselective acylation of substrates 2, 3 and 4 via lipase catalysis has not previously been reported. Herein, we report a study on the preparation of such alkyl c-substituted primary alcohols in high enantiomeric purity via enzymatic resolution.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Lipase catalyzed acylation of primary alcohols with remotely located stereogenic centres: the resolution of (±)-4,4-dimethyl-3-phenyl-1-pentanol

Sabbani

Hedenström

Andersson

2007

Tetrahedron: Asymmetry

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Section: Resultsmentioning

confidence: 84%

Section: Introductionmentioning

confidence: 99%

Lipase catalyzed acylation of primary alcohols with remotely located stereogenic centres: the resolution of (±)-4,4-dimethyl-3-phenyl-1-pentanol

Sabbani

Hedenström

Andersson

2007

Tetrahedron: Asymmetry

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“…Lipases from Pseudomonas cepacia, Candida rugosa, and Candida antarctica have been used in secondary alcohol resolution. [12][13][14][15] Vinyl esters are commonly used as acyl donors for irreversible acylation. Hirose et al [12] demonstrated the effective kinetic resolution of 2-phenyl-1-propanol by using an acyl donor, vinyl 3-phenylbutanoate.…”

Section: Introductionmentioning

confidence: 99%

Optimization of Lipase-Catalyzed Enantioselective Production of 1-Phenyl 1-Propanol Using Response Surface Methodology

Soyer¹,

Bayraktar²,

Mehmetoǧlu³

2010

Preparative Biochemistry and Biotechnology

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Optically active 1-phenyl 1-propanol is used as a chiral building block and synthetic intermediate in the pharmaceutical industries. In this study, the enantioselective production of 1-phenyl 1-propanol was investigated systematically using response surface methodology (RSM). Before RSM was applied, the effects of the enzyme source, the type of acyl donor, and the type of solvent on the kinetic resolution of 1-phenyl 1-propanol were studied. The best results were obtained with Candida antartica lipase (commercially available as Novozym 435), vinyl laurate as the acyl donor, and isooctane as the solvent. In the RSM, substrate concentration, molar ratio of acyl donor to the substrate, amount of enzyme, temperature, and stirring rate were chosen as independent variables. The predicted optimum conditions for a higher enantiomeric excess (ee) were as follows: substrate concentration, 233 mM; molar ratio of acyl donor to substrate, 1.5; enzyme amount, 116 mg; temperature, 47 °C; and stirring rate, 161 rpm. A verification experiment conducted at these optimized conditions for maximum ee yielded 91% for 3 hr, which is higher than the predicted value of 83%. The effect of microwave on the ee was also investigated and ee reached 87% at only 5 min.

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“…Kawasaki et al have reported a highly efficient kinetic resolution protocol for various primary alcohols. [15] A KR system incorporating a lipase from Burkholderia cepacia in the presence of differently substituted vinyl 3-phenylpropanoates as acyl donors was found to be the most selective. Encouraged by their findings, we investigated the DKR of the chosen model substrate 2a in an initial screening.…”

mentioning

confidence: 99%

Dynamic Kinetic Resolution of Primary Alcohols with an Unfunctionalized Stereogenic Center in the β‐Position

et al. 2007

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Primary alcohols with an unfunctionalized stereogenic center in the b-position undergo an enzyme-and metal-catalyzed dynamic kinetic resolution (DKR). The in situ racemization of the primary alcohol, required for the DKR, takes place via: (i) ruthenium-catalyzed dehydrogenation of the alcohol, (ii) enolization of the aldehyde formed, and (iii) ruthenium-catalyzed readdition of hydrogen to the aldehyde. The present method widens the scope of metal-and enzyme-catalyzed DKR, which has so far been limited to a-chiral alcohol and amine derivatives.Keywords: dynamic kinetic resolution; enzyme catalysis; metal catalysis; primary alcohols The development of efficient protocols for the synthesis of optically active compounds has attracted major attention in organic chemistry, because of the increasing demand for such compounds as building blocks in the pharmaceutical or agrochemical industry.[1] The most common way to prepare enantiomerically pure compounds in the chemical industry is still via resolution and separation of enantiomers from racemic mixtures.[2] In this respect, enzymatic resolution plays an important and dominant role [3] and a number of multi-ton industrial processes are based on enzymatic resolution.[4] A drawback with these kinetic resolutions (KR) is the maximum theoretical yield of 50 % leading to waste of half of the material. A solution to this problem is dynamic kinetic resolution (DKR), [5] which takes advantage of an in situ racemization of the remaining substrate enantiomer (Scheme 1). In this way a yield of up to 100 % of enantiopure material can be achieved.During the past decade, various DKR methods based on the combination of an enzyme and an additional racemization catalyst have been developed. [5d,6] In particular, the combination of an enzyme and a transition metal catalyst has proven to be useful for DKR of secondary alcohols.[5d] In the first efficient system developed, [7] Shvos ruthenium catalyst 1 (Scheme 2) was employed, and this catalyst requires a slightly elevated temperature. This procedure has been successfully applied to the DKR of various substituted secondary alcohols including diols [8] and allylic alcohols.[9] The method was recently extended to amines. [10] Further developments have led to room temperature procedures for DKR of secondary alcohols that employ a new type of racemization catalyst together with an enzyme. [11][12][13] In all these applications, the metal catalyst can be compared with the dehydrogenase/hydrogenase activity by enzymes having NAD(P)/ NAD(P)H as cofactor.All of the protocols for chemoenzymatic DKR of alcohols and amines described to date have been limited to substrates that are chiral at the a-carbon (A, Figure 1). An extension of chemoenzymatic DKR to alcohols and amines with a non-functionalized chiral carbon, for example, B (Figure 1) would significantly broaden the scope of the method. Scheme 1. Principle of a dynamic kinetic resolution (DKR).Adv. Synth. Catal. 2007, 349, 1577 -1581 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim...

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The effect of vinyl esters on the enantioselectivity of the lipase-catalysed transesterification of alcohols

Cited by 62 publications

References 36 publications

Lipase catalyzed acylation of primary alcohols with remotely located stereogenic centres: the resolution of (±)-4,4-dimethyl-3-phenyl-1-pentanol

Lipase catalyzed acylation of primary alcohols with remotely located stereogenic centres: the resolution of (±)-4,4-dimethyl-3-phenyl-1-pentanol

Optimization of Lipase-Catalyzed Enantioselective Production of 1-Phenyl 1-Propanol Using Response Surface Methodology

Dynamic Kinetic Resolution of Primary Alcohols with an Unfunctionalized Stereogenic Center in the β‐Position

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