Oxidative Cleavage Of Vicinal Diols Research Articles

Vanadium Catalyst in Micelles: Toward a Greener Aerobic Oxidative Cleavage of Vicinal Diols in Water

Aqueous micellar media offer an alternative to organic solvents for the development of safe and environmentally benign synthesis. A vanadium aminotriphenolate complex, known to be an effective catalyst for the aerobic oxidative C–C cleavage of vicinal diols in organic solvents, was incorporated in zwitterionic dodecyl phosphocholine (DPC) and in mixed TPGS-750-M:DPC micelles. It efficiently performed affording the corresponding carbonyl derivatives with no overoxidation, with catalyst loading down to 0.2 mol % and reaching TONs up to 500. The mixed micelles, which combine the enhanced stability conferred by zwitterionic DPC and the exceptional extraction properties of non-ionic TPGS-750-M, could be recycled and full conversion achieved upon reloading with catalyst and substrate. The study of the correlation between the reactivity of different substrates and their local concentration in the micellar core, derived from DOSY experiments, highlights that, while lipophilicity is important, the ease with which the substrate can access the catalyst, and therefore the location of the catalyst in the micellar phase, must also be considered when trying to rationalize reactivity in micelles.

Cover Feature: Oxidative Cleavage of Vicinal Diols Catalyzed by Monomeric Fe‐Sites Inside MFI Zeolite (ChemCatChem 21/2022)

The Cover Feature shows the monomeric iron on MFI zeolite as an efficient catalyst for the oxidative cleavage of vicinal diols, while the oligomeric/bulk iron species lack activity. In their Full Paper, E. Saraçi and co-workers explore the Fe/MFI catalysts for the oxidative cleavage of ethylene glycol. Further vicinal diols, often found in biomass, where also tested. The iron species present were correlated with corresponding reaction rates revealing that monomeric Fe species inside zeolite MFI were responsible for the oxidative cleavage of C–C bonds of vicinal diols. The recyclability of the catalyst and reaction mechanism were also studied. More information can be found in the Full Paper by E. Saraçi and co-workers.

Oxidative Cleavage of Vicinal Diols Catalyzed by Monomeric Fe‐Sites Inside MFI Zeolite

AbstractThe oxidative cleavage of vicinal diols to carboxylic acids was investigated over heterogeneous Fe/MFI catalysts in aqueous medium, with green oxidant H2O2 and in mild reaction conditions. High conversions and selectivities (X=90 %, S=79 %) were achieved for the oxidative cleavage of ethylene glycol. Further substrates were also tested broadening the relevance of this catalyst. The employment of non‐noble and abundant Fe as the active metal and the MFI‐type zeolite as support has a clear advantage over the presently used homogeneous or noble metal‐based catalysts. A combination of complementary characterisation techniques with catalytic results is used to show that monomeric Fe species inside zeolite MFI are the active sites for the oxidative cleavage of C−C bonds of vicinal diols. The recyclability of the catalyst and reaction mechanism were also studied.

The product-controllable aerobic oxidative cleavage of vicinal diols using vanadium-based photocatalysts

A method for the photocatalytic controllable oxidative cleavage of C–C bonds is developed with molecular oxygen as the oxidant.

Heterogeneous carbon nitride photocatalyst for C–C bond oxidative cleavage of vicinal diols in aerobic micellar medium

A visible-light promoted oxidative cleavage of vicinal diols by using CN620 as a recyclable photocatalyst in aerobic micellar medium has been developed.

Chitosan: The One and Only? Aminated Cellulose as an Innovative Option for Primary Amino Groups Containing Polymers.

The aim of this study was the synthesis and in vitro characterization of aminated cellulose as alternative excipient to chitosan. The aldehyde form of cellulose was generated via the oxidative cleavage of vicinal diols by the addition of increasing concentrations of sodium periodate. The insertion of primary amines was achieved by reductive amination with ammonia. The degree of substitution was calculated via primary amino group quantification using a 2,4,6-trinitrobenzenesulfonic acid assay. Mucoadhesiveness was examined by adopting the rotating-cylinder method and tensile studies using porcine intestinal mucosa. Hydration was evaluated at pH 2-11. The successful formation of aldehydes as well as a subsequent introduction of up to 311.61 micromoles per gram of primary amines were proven to correlate with the amount of added periodate. There was a 3- to 14-fold prolongation in the mucosal residence time of the new polymer in comparison to chitosan, as measured by the rotating-cylinder method. Although cationic cellulose did not reach the maximum detachment force of chitosan, the total work of adhesion of the newly synthesized cellulose derivate was higher than that of chitosan. The higher the degree of amination, the higher the degree of hydration in neutral and alkaline aqueous media was. Compared to chitosan, the novel cationic cellulose derivative displays improved mucoadhesive properties as well as sufficient hydration at physiological pH. Therefore, aminated cellulose is a promising alternative to the cationic polymers, such as chitosan, used thus far.

Cover Picture: Efficient Vanadium‐Catalyzed Aerobic C−C Bond Oxidative Cleavage of Vicinal Diols (Adv. Synth. Catal. 17/2018)

Cover Picture: Efficient Vanadium‐Catalyzed Aerobic C−C Bond Oxidative Cleavage of Vicinal Diols (Adv. Synth. Catal. 17/2018)

New perspectives of starch: Synthesis and in vitro assessment of novel thiolated mucoadhesive derivatives

AimThe purpose of this study was to develop a novel thiolated starch polymer with improved mucoadhesive properties by conjugation of cysteamine to starch as a natural polymer of restricted mucoadhesive properties. MethodsAldehyde substructures were integrated into starch via oxidative cleavage of vicinal diols by increasing amounts of sodium periodate followed by covalent attachment of cysteamine to oxidized starch via reductive amination. Thiol groups were quantified via Ellman’s reaction and their impact on mucoadhesion was analyzed by rheological investigations, the rotating cylinder method and tensile studies on porcine mucosa. ResultsThe total amount of immobilized thiol groups revealed a correlation between degree of oxidation and thiolation. Modified starch demonstrated an up to 1.66-fold increase in water uptake in comparison to native starch. Modification of starch resulted in greatly improved cohesive properties and improvement in mucoadhesion. Rheological investigations revealed a 2- to 4-fold rise in viscosity of mucus. Tensile studies revealed a linear correlation between degree of oxidation/thiolation and enhancement of maximum detachment force and total work adhesion. ConclusionIn terms of these results, thiolated starch is a new, promising, polymer in the field of mucoadhesive drug delivery systems.

Oxidative Cleavage of Vicinal Diols with the Combination of Platinum and Vanadium Catalysts and Molecular Oxygen

AbstractThe combination of Pt/C and V2O5 catalysts gave good performance for the oxidative cleavage of trans‐1,2‐cyclohexanediol into adipic acid via 2‐hydroxycyclohexanone. The yield of adipic acid reached 90 % in the one‐pot oxidative cleavage of trans‐1,2‐cyclohexanediol. The yield was higher than that obtained in the oxidation of 2‐hydroxycyclohexanone with V catalyst, and the higher yield was due to the low 2‐hydroxycyclohexanone concentration during the one‐pot oxidation of trans‐1,2‐cyclohexanediol. Cyclic vicinal diols having a six‐membered ring and linear vicinal diols having two secondary OH groups were converted into dicarboxylic acids and two carboxylic acids, respectively. The activity of the Pt catalyst decreased during the reaction, and the activity was partially restored by treating the used catalyst with H2 at 573 K. Even without regeneration, the turnover number based on total Pt could reach ≈1000 in a long reaction with an increased amount of trans‐1,2‐cyclohexanediol.

Nanofibers of cellulose and its derivatives fabricated using direct electrospinning.

A short review with 49 references describes the electrospinninng (ES) process for polysaccharides, cellulose and chitosan, and their derivatives, including cellulose acetate and hydroxypropyl cellulose. A majority of applied studies adopted a two step-process, in which the cellulose acetate was used for the first ES process, followed by acetyl group removal to regenerate cellulose thin fibers. The electrospun nonwoven fabrics (ESNW) of regenerated cellulose can be modified by introduction of aldehyde groups by oxidative cleavage of vicinal diols using periodates, and these aldehyde groups serve as acceptors of foreign substances, with various chemical/biological functions, to be immobilized on the fiber surfaces in the ESNW matrices. Direct electrospinning of cellulose from trifluroacetic acid solution was also developed and the applied studies were summarized to conclude the current trends of interests in the ES and related technologies.

ChemInform Abstract: Nitroxyl Radical/PhI(OAc)2: One‐Pot Oxidative Cleavage of Vicinal Diols to (Di)carboxylic Acids.

AbstractA mild and efficient method for the conversion of terminal and internal 1,2‐diols to carboxylic acids is presented which proceeds without epimerization.

Nitroxyl Radical/PhI(OAc)2: One-Pot Oxidative Cleavage of Vicinal Diols to (Di)Carboxylic Acids

A mild and user-friendly one-pot oxidative cleavage of vicinal diols to their corresponding (di)carboxylic acids using AZADOs and PhI(OAc)(2) is described. 1,2-Diols and 2,3-diols as well as 1,2,3-triol gave one- or two-carbon-unit-shorter carboxylic acids. Internal vicinal diols also smoothly underwent one-pot oxidative cleavage to afford the corresponding dicarboxylic acids. Cyclic vicinal diols are converted to their corresponding open-form dicarboxylic acids.

ChemInform Abstract: On‐Column Solvent‐Free Oxidative Cleavage Reactions of Vicinal Diols by Silica Gel and Paraperiodic Acid: Application to in situ Sequential Oxidation and Knoevenagel Reactions.

AbstractThe on‐column oxidative cleavage of vicinal diols proceeds without the need for toxic, volatible organic solvents or aqueous work‐up and does not require pre‐preparation of the supported oxidant.

ChemInform Abstract: An Original On‐Column Oxidative Cleavage of Vicinal Diols Using Alumina/Potassium Periodate: Application to Sequential Oxidation/Horner—Emmons Reactions.

ChemInformVolume 43, Issue 2 Preparative Organic Chemistry ChemInform Abstract: An Original On-Column Oxidative Cleavage of Vicinal Diols Using Alumina/Potassium Periodate: Application to Sequential Oxidation/Horner—Emmons Reactions. Saada C. Dakdouki, Saada C. Dakdouki Lab. Chim. Mol. Thio-Org., CNRS, Ec. Natl. Super. Ing., Univ. Caen, F-14050 Caen, Fr.Search for more papers by this authorDidier Villemin, Didier Villemin Lab. Chim. Mol. Thio-Org., CNRS, Ec. Natl. Super. Ing., Univ. Caen, F-14050 Caen, Fr.Search for more papers by this authorNathalie Bar, Nathalie Bar Lab. Chim. Mol. Thio-Org., CNRS, Ec. Natl. Super. Ing., Univ. Caen, F-14050 Caen, Fr.Search for more papers by this author Saada C. Dakdouki, Saada C. Dakdouki Lab. Chim. Mol. Thio-Org., CNRS, Ec. Natl. Super. Ing., Univ. Caen, F-14050 Caen, Fr.Search for more papers by this authorDidier Villemin, Didier Villemin Lab. Chim. Mol. Thio-Org., CNRS, Ec. Natl. Super. Ing., Univ. Caen, F-14050 Caen, Fr.Search for more papers by this authorNathalie Bar, Nathalie Bar Lab. Chim. Mol. Thio-Org., CNRS, Ec. Natl. Super. Ing., Univ. Caen, F-14050 Caen, Fr.Search for more papers by this author First published: 15 December 2011 https://doi.org/10.1002/chin.201202036Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume43, Issue2January 10, 2012 RelatedInformation

An Original On‐Column Oxidative Cleavage of Vicinal Diols Using Alumina/Potassium Periodate: Application to Sequential Oxidation/Horner–Emmons Reactions

AbstractAn unprecedented simple on‐column solvent‐free oxidative cleavage of vicinal diols in the solid phase using alumina/potassium metaperiodate is described herein. It permits preparation of the corresponding carbonyl compounds with high purity and good to excellent yields requiring only short reaction times. This methodology is then employed in on‐column sequential oxidation/Horner–Emmons reactions for the preparation of selected stilbenes in good yields where both reaction and purification are integrated in a single unit or occur simultaneously permitting the rapid and easy preparation of small samples of pure stilbenes.

Positive Effects of Ionic Liquids in the Oxidative Cleavage of vic-diols Catalyzed by Mn(III) Complexes

The obtaining of aldehydes or ketones through oxidative cleavage of vicinal diols requires the use of a catalyst. In this work we present the positive effects of ionic liquids in the homogeneous oxidative cleavage of ethylenglycol, pinacol, benzopinacol and hydrobenzoin, catalyzed by Mn(salen) complexes. The catalyst dissolved in ionic liquids allows high efficiency (yield up to 99% with air as oxidant), low environmental impact and, in addition, it is possible to recycle. In order to understand the role of the catalyst and of the ionic liquids, DFT studies were performed and a possible catalytic cycle is presented.

Oxidation of Cyclohexanediol Derivatives with 12-Tungstophosphoric Acid-Hydrogen Peroxide System

Oxidation of cyclohexanediol derivatives with 12-tungstophospholic acid-hydrogen peroxide system was investigated focusing on a reaction mechanism in the preparation of dicarboxylic acids from olefin because oxidative cleavage of vicinal diols would be a rate-determining step in oxidative cleavage of carbon-carbon double bonds. trans-1,2-Cyclohexanediol (DHC) was converted to adipic acid almost quantatively, while 1-hydroxy-2-methoxycyclohexane (HMC) gave a mixture of adipic acid, glutaric acid and monomethyl adipate. In the case of 1,4-cyclohexanediol, 4-hydroxy-cyclohexanone and many hyperoxidated products were obtained. Based on results for HMC, it is concluded that following route would be also reasonable in oxidative cleavage of vicinal diol with 12-tungstophospholic acid-hydrogen peroxide system: (1) first oxidation of vicinal diol to alpha-hydroxyketone, (2) nucleophilic attack of hydrogen peroxide attacks to carbonyl carbon, (3) Baiyer-Villiger rearrangement of dihydroxy-hydroperoxide to a cyclic ester, (4) hydrolysis and final oxidation to dicarboxylic acid.

Oxidative cleavage of vic-diols catalyzed by manganese (III) complexes in ionic liquids

Abstract The oxidative cleavage of vicinal diols allows the selective oxidation of diols in order to obtain aldehydes or ketones. In this work we present a novel catalytic system based on Mn III (salen) complexes dissolved in ionic liquids that allows high efficiency with low environmental impact in the oxidative cleavage of ethyleneglycol, pinacol, benzopinacol and hydrobenzoin. The use of ionic liquids in this reaction shows a positive effect of the solvent in the efficiency of the Mn III catalysts (increase of the yield in ionic liquids: 10–60%).

Oxidative cleavage of vicinal diols: IBX can do what Dess–Martin periodinane (DMP) can

The fact that IBX exhibits reactivity akin to DMP is demonstrated from the results observed with strained and sterically hindered syn 1,2-diols, which undergo oxidative cleavage via a 12-I-5 spirobicyclic periodinane. The use of TFA, a protonating solvent, promotes the formation of the 12-I-5 intermediate for 1,2-diols of all types (sec,sec, sec,tert and tert,tert), leading to efficient oxidative fragmentation.

Reaction of tin porphyrins with vicinal diols.

Reactions of tin porphyrins with vicinal diols were investigated. Treatment of (TTP)Sn(CCPh)(2) or (TTP)Sn(NHtolyl)(2) with pinacol and 2,3-diphenylbutane-2,3-diol afforded diolato complexes (TTP)Sn[OC(Me)(2)C(Me)(2)O] (1) and (TTP)Sn[OC(Ph)(Me)C(Ph)(Me)O] (2), respectively. Both complexes underwent C-C cleavage reactions to give (TTP)Sn(II) and ketones. Reaction of (TTP)Sn(CCPh)(2) with 1 equivalent of o-catechol generated (TTP)Sn(CCPh)(OC(6)H(4)OH) (3), which subsequently transformed into (TTP)Sn(OC(6)H(4)O) (4). With excess catechol, disubstituted (TTP)Sn(OC(6)H(4)OH)(2) (5) was obtained. (TTP)Sn(CCPh)(OCHRCHROH) (R = H, 6; R = Ph, 8) and (TTP)Sn(OCHRCHROH)(2) (R = H, 7; R = Ph, 9) were obtained analogously by treatment of (TTP)Sn(CCPh)(2) with appropriate diols. In the presence of dioxygen, tin porphyrin complexes were found to promote the oxidative cleavage of vicinal diols and the oxidation of alpha-ketols to alpha-diketones. Possible reaction mechanisms involving diolato or enediolato intermediates are discussed. The molecular structure of (TTP)Sn(CCPh)(OC(6)H(4)OH) (3) was determined by X-ray crystallography.