Application of chemoenzymatic hydrolysis in the synthesis of 2-monoacylglycerols

Whitten, Kyle M.; Makriyannis, Alexandros; Vadivel, Subramanian K.

doi:10.1016/j.tet.2012.04.101

Cited by 11 publications

(8 citation statements)

References 39 publications

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“…To the best of our knowledge the chemoenzymatic synthesis of this endogenous substance is reported here for the first time and parallels those we reported earlier for the endocannabinoid lipid 2-AG and its analogs. 33,34 Importantly, our approach provides the 2-PGE 2 -G essentially free of 1(3)-acylglycerol rearrangement byproducts as confirmed by 1 H NMR data. In a previous study on the metabolism of prostaglandin glycerol esters the 2-PGE 2 -G was the minor product which was synthesized as a mixture with the 1(3) regioisomer in a ratio 1:9.…”

Section: Resultssupporting

confidence: 55%

Design and synthesis of novel prostaglandin E2 ethanolamide and glycerol ester probes for the putative prostamide receptor(s)

Shelnut

Nikas

Finnegan

et al. 2015

Tetrahedron Letters

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Novel prostaglandin-ethanolamide (PGE2-EA) and glycerol ester (2-PGE2-G) analogs were designed and synthesized to aid in the characterization of a putative prostamide receptor. Our design incorporates the electrophilic isothiocyanato and the photoactivatable azido groups at the terminal tail position of the prototype. Stereoselective Wittig and Horner–Wadsworth–Emmons reactions install the head and the tail moieties of the PGE2 skeleton. The synthesis is completed using Mitsunobu azidation and peptide coupling as the key steps. A chemoenzymatic synthesis for the 2-PGE2-G is described for first time.

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Section: Resultssupporting

confidence: 55%

Design and synthesis of novel prostaglandin E2 ethanolamide and glycerol ester probes for the putative prostamide receptor(s)

Shelnut

Nikas

Finnegan

et al. 2015

Tetrahedron Letters

Self Cite

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“…To date, 2-AG is synthesized by either chemical [16][17][18][19] or chemoenzymatic methods To date, 2-AG is synthesized by either chemical [16][17][18][19] or chemoenzymatic methods [20][21][22][23]. The chemical methods described for the synthesis of 2-AG are based on the same procedure: acylation of suitable 1,3-protected glycerol, or glycidol, precursors with an activated arachidonic acid derivative, followed by deprotection and separation of the isomeric arachidonoylglycerols.…”

Section: -Arachidonoylglycerol (2-agmentioning

confidence: 99%

“…The enzymatic methods described for the synthesis of 2-AG are based on a two-step enzymatic process [20][21][22][23]. 1,3-Dibutyrylglycerol is synthesized by selective esterification of glycerol, using vinyl butyrate in the presence of immobilized Candida antarctica lipase B and anhydrous dichloromethane as solvent.…”

Section: -Arachidonoylglycerol (2-agmentioning

confidence: 99%

2-Arachidonoylglycerol Synthesis: Facile and Handy Enzymatic Method That Allows to Avoid Isomerization

Ottria

Casati²,

Rota³

et al. 2022

Molecules

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A simple and practical synthesis of 2-arachidonoyl glycerol (2-AG), an endogenous agonist for cannabinoid receptors, based on a two-step enzymatic process and a chemical coupling, was achieved with a good yield and negligible amount of the isomerization product 1-AG. Commercial preparation of immobilized lipase from Mucor miehei (MML) was selected as the most suitable enzyme to catalyze the efficient protection of glycerol using vinyl benzoate as an acyl transfer reagent in tetrahydrofuran. The same enzyme was used to remove the protective groups in positions 1 and 3. Owing to the mild neutral conditions and easy suitability of the method, 2-AG was obtained without any isomerization to the more stable 1-AG and air oxidation of acid chain. The synthetic method proposed here allows us to easily obtain 2-AG from the protected precursor in a one-step reaction without purification requirement.

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“…A few methods have been developed for the synthesis of 2-MAG. − However, acyl migration during reactions is the major impediment for the preparation of highly pure 2-MAGs. It has been reported that the ratio of 2-MAG to 1-MAG under equilibrium conditions is 1:9, suggesting that the spontaneous isomerization of 2-MAG will occur to form the more stable 1-MAG under certain conditions. , Acyl migration is a universal phenomenon during the alcoholysis and esterification with partial acylglycerols as a substrate or a product of the reaction.…”

Section: Introductionmentioning

confidence: 99%

Effect of Solvent on Acyl Migration of 2-Monoacylglycerols in Enzymatic Ethanolysis

Wang

Zhao

Yang

et al. 2020

J. Agric. Food Chem.

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Acyl migration occurs in many reactions and is the main obstacle for structured lipid synthesis. In this study, 2-monoacylglycerol (2-MAG) was prepared by enzymatic ethanolysis in three different media to evaluate the effect of environment on product composition. The contents of 2-MAG obtained in ethanol, hexane + ethanol, and t-butanol + ethanol systems were 30.6, 15.7, and 32.4%, respectively, after 3 h reaction. Afterward, the acyl migration kinetics of 2-MAG were studied in solvent and solventless systems without the use of lipase. Results indicate that 2-MAG in the solventless system had the highest acyl migration rate. The isomerization was efficiently prevented by the use of polar solvents, especially t-butanol. The rate constants were shown to be the highest and activation energy values were the lowest in solventless systems. The novel finding in this study was that solvent had inhibitory effect on 2-MAG isomerization, but the nonpolar hexane had the lowest inhibition of acyl migration compared to other solvents.

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Application of chemoenzymatic hydrolysis in the synthesis of 2-monoacylglycerols

Cited by 11 publications

References 39 publications

Design and synthesis of novel prostaglandin E2 ethanolamide and glycerol ester probes for the putative prostamide receptor(s)

Design and synthesis of novel prostaglandin E2 ethanolamide and glycerol ester probes for the putative prostamide receptor(s)

2-Arachidonoylglycerol Synthesis: Facile and Handy Enzymatic Method That Allows to Avoid Isomerization

Effect of Solvent on Acyl Migration of 2-Monoacylglycerols in Enzymatic Ethanolysis

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