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4-Methyltetrahydropyran (4-MeTHP): Application as an Organic Reaction Solvent.

ABSTRACT: 4-Methyltetrahydropyran (4-MeTHP) is a hydrophobic cyclic ether with potential for industrial applications. We herein report, for the first time, a comprehensive study on the performance of 4-MeTHP as an organic reaction solvent. Its broad application to organic reactions includes radical, Grignard, Wittig, organometallic, halogen-metal exchange, reduction, oxidation, epoxidation, amidation, esterification, metathesis, and other miscellaneous organic reactions. This breadth suggests 4-MeTHP can serve as a substitute for conventional ethers and harmful halogenated solvents. However, 4-MeTHP was found incompatible with strong Lewis acids, and the C-O bond was readily cleaved by treatment with BBr3 . Moreover, the radical-based degradation pathways of 4-MeTHP, THP and 2-MeTHF were elucidated on the basis of GC-MS analyses. The data reported herein is anticipated to be useful for a broad range of synthetic chemists, especially industrial process chemists, when selecting the reaction solvent with green chemistry perspectives.

SUBMITTER: Kobayashi S

PROVIDER: S-EPMC6916367 | biostudies-literature | 2019 Nov

REPOSITORIES: biostudies-literature

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4-Methyltetrahydropyran (4-MeTHP): Application as an Organic Reaction Solvent.

Kobayashi Shoji S Tamura Tomoki T Yoshimoto Saki S Kawakami Takashi T Masuyama Araki A

Chemistry, an Asian journal 20191016 21

4-Methyltetrahydropyran (4-MeTHP) is a hydrophobic cyclic ether with potential for industrial applications. We herein report, for the first time, a comprehensive study on the performance of 4-MeTHP as an organic reaction solvent. Its broad application to organic reactions includes radical, Grignard, Wittig, organometallic, halogen-metal exchange, reduction, oxidation, epoxidation, amidation, esterification, metathesis, and other miscellaneous organic reactions. This breadth suggests 4-MeTHP can ...[more]

PMID: 31549485

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Project description:Biocatalysis has emerged as an important tool in synthetic organic chemistry enabling the chemical industry to execute reactions with high regio- or enantioselectivity and under usually mild reaction conditions while avoiding toxic waste. Target substrates and products of reactions catalyzed by carboxylic ester hydrolases are often poorly water soluble and require organic solvents, whereas enzymes are evolved by nature to be active in cells, i.e., in aqueous rather than organic solvents. Therefore, biocatalysts that withstand organic solvents are urgently needed. Current strategies to identify such enzymes rely on laborious tests carried out by incubation in different organic solvents and determination of residual activity. Here, we describe a simple assay useful for screening large libraries of carboxylic ester hydrolases for resistance and activity in water-miscible organic solvents. We have screened a set of 26 enzymes, most of them identified in this study, with four different water-miscible organic solvents. The triglyceride tributyrin was used as a substrate, and fatty acids released by enzymatic hydrolysis were detected by a pH shift indicated by the indicator dye nitrazine yellow. With this strategy, we succeeded in identifying a novel highly organic-solvent-tolerant esterase from Pseudomonas aestusnigri In addition, the newly identified enzymes were tested with sterically demanding substrates, which are common in pharmaceutical intermediates, and two enzymes from Alcanivorax borkumensis were identified which outcompeted the gold standard ester hydrolase CalB from Candida antarcticaIMPORTANCE Major challenges hampering biotechnological applications of esterases include the requirement to accept nonnatural and chemically demanding substrates and the tolerance of the enzymes toward organic solvents which are often required to solubilize such substrates. We describe here a high-throughput screening strategy to identify novel organic-solvent-tolerant carboxylic ester hydrolases (CEs). Among these enzymes, CEs active against water-insoluble bulky substrates were identified. Our results thus contribute to fostering the identification and biotechnological application of CEs.

Dataset Information

4-Methyltetrahydropyran (4-MeTHP): Application as an Organic Reaction Solvent.

Publications

4-Methyltetrahydropyran (4-MeTHP): Application as an Organic Reaction Solvent.

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