Cyclization of citronellal is a necessary intermediate step to produce the important flavor chemical (-)-menthol. Here, a continuous-flow Pickering emulsion (FPE) strategy for selective cyclization of citronellal to (-)-isopulegol by using water droplets hosting a heteropolyacid (HPA) catalyst to fill a column reactor is demonstrated. Owing to the large liquid-liquid interface and the excellent confinement ability of droplets toward HPA, the FPE system exhibited a much higher catalysis efficiency than its batch counterpart (2-5-fold) and an excellent durability (two months). Moreover, a remarkably enhanced selectivity was observed from 34.8 % for batch reactions to 64 % for the FPE reactions. It was found that the water droplet size and the flow rate significantly impact the catalysis selectivity and efficiency. This study not only represents an unprecedented and sustainable process for the selective cyclization of citronellal but also demonstrates a new flow-interface catalysis effect that can be useful for designing innovative catalysis systems in the future.
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http://dx.doi.org/10.1002/cssc.201700318 | DOI Listing |
ACS Org Inorg Au
August 2024
Laboratory for Chemistry and Life Science, Institute of Innovative Research, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan.
Linear monoterpenes, versatile reaction biosubstrates, are bound and subsequently converted to various cyclic monomers and oligomers with excellent selectivity and efficiency, in natural enzymes. We herein report bioinspired functions of synthetic polyaromatic cavities toward linear monoterpenes in the solution and solid states. The cavities are provided by polyaromatic coordination capsules, formed by the assembly of Pt(II) ions and bent bispyridine ligands with two anthracene panels.
View Article and Find Full Text PDFInorg Chem
August 2024
Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education, Faculty of Chemistry, Northeast Normal University, Changchun 130024, P. R. China.
The host effect of the supramolecular [GaL] tetrahedral metallocage on Prins cyclization reaction of the substrate by encapsulated citronellal has been investigated by means of molecular dynamics and quantum mechanics. The encapsulation process of the substrate into the [GaL] cavity was simulated via attach-pull-release (APR) methods. Thermodynamic calculations and classical molecular dynamics simulations assessed the substrate's microenvironment inside the cavity, guiding DFT-level modeling of the reaction.
View Article and Find Full Text PDFDalton Trans
February 2023
Department of Chemistry and Biochemistry, The Ohio State University, 100 West 18th Ave, Columbus, OH 43210, USA.
A palladium diphosphine pincer complex H(PNP-PdI) has been encapsulated in the benzotriazolate metal-organic framework MFU-4-OH ([Zn(OH)(btdd)], btdd = bis(1,2,3-triazolo)dibenzodioxin), and the resulting materials were investigated as Lewis acid catalysts for cyclization of citronellal to isopulegol. Rapid catalyst immobilization is facilitated by a Brønsted acid-base reaction between the H(PNP-PdI) benzoic acid substituents and Zn-OH groups at the framework nodes. Catalyst loading can be controlled up to a maximum of 0.
View Article and Find Full Text PDFBeilstein J Org Chem
March 2022
Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca' Foscari di Venezia, via Torino 155, 30172, Mestre-Venezia, Italy.
The hexameric resorcin[4]arene capsule as a self-assembled organocatalyst promotes a series of reactions like the carbonyl-ene cyclization of citronellal preferentially to isopulegol, the water elimination from 1,1-diphenylethanol, the isomerization of α-pinene and β-pinene preferentially to limonene and minor amounts of camphene. The role of the supramolecular catalyst consists in promoting the protonation of the substrates leading to the formation of cationic intermediates that are stabilized within the cavity with consequent peculiar features in terms of acceleration and product selectivity. In all cases the catalytic activity displayed by the hexameric capsule is remarkable if compared to many other strong Brønsted or Lewis acids.
View Article and Find Full Text PDFJ Agric Food Chem
September 2021
Université Claude Bernard Lyon 1/CNRS. Institut de Chimie et Biochimie Moléculaires et Supramoléculaires, (ICBMS), 1 rue Victor Grignard, 69100 Villeurbanne, France.
Vector-borne diseases cause around 700,000 deaths every year. Insect repellents are one of the strategies to limit them. -menthane-3,8-diol (PMD), a natural compound, is one of the most promising alternatives to conventional synthetic repellents.
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