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Post-functionalization of dibenzothiophene to functionalized biphenyls via a photoinduced thia-Baeyer-Villiger oxidation.

ABSTRACT: The Baeyer-Villiger reaction is used extensively in organic chemistry. Sila- and bora-variants have also been documented widely, with these processes underpinning, for example, the Fleming-Tamao oxidation and hydroborative alkene hydration, respectively. By contrast, the development of thia-Baeyer-Villiger reactions involving sulfoxides has long been considered unlikely because competitive oxidation to the sulfone occurs exclusively. Here, we disclose a photoinduced thia-Baeyer-Villiger-type oxidations; specifically, we find that exposure of dibenzothiophene (DBT) derivatives to an iron porphyrin catalyst under Ultraviolet irradiation in the presence of t-BuOOH generates sulfinic esters in up to 87% yield. The produced sulfinic esters are transformed to a variety of biphenyl substrates including biphenyl sulfoxides, sulfones and sulfonamides in 1-2 steps. These results provide a mild process for the selective functionalization of sulfur compounds, and offer a biomimetic approach to convert DBT into 2-hydroxybiphenyl under controllable stepwise pathway. Based upon experimental evidences and DFT calculation, a mechanism is proposed.

SUBMITTER: Ma X

PROVIDER: S-EPMC7021910 | biostudies-literature |

REPOSITORIES: biostudies-literature

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A nonenzymatic acid/peracid catalytic cycle for the Baeyer-Villiger oxidation.

Project description:The combined action of carbodiimide and hydrogen peroxide upon exposure to carboxylic acid catalysts serves to generate transient peracids that can be engaged in the Baeyer-Villiger rearrangement of ketones to lactones. Up to 35 turnovers of the catalytic cycle may be achieved. The conditions are especially useful in the context of reactive cyclohexanones, and allow the use of H2O2 as the terminal oxidant. A singular example of a chiral catalyst demonstrates, in principle, that enantioselective catalysis will be possible with this strategy for catalyst turnover.

| S-EPMC4125978 | biostudies-literature

Keggin-Type Heteropoly Salts as Bifunctional Catalysts in Aerobic Baeyer-Villiger Oxidation.

Project description:The cobalt, manganese, and iron salts of tungstophosphoric or molybdophosphoric acid with growing content of metals were applied for the first time as catalysts in the Baeyer-Villiger (BV) oxidation of cyclohexanone to ?-caprolactone with molecular oxygen. The catalysts were characterized with Fourier transform infrared spectroscopy (FTIR), X-ray fluorescence (XRF), and ethanol decomposition reaction. Introduction of transition metals into the heteropoly structure increases the activity of resulting heteropoly salts in comparison with parent heteropolyacids. It was shown that the most active catalysts are salts of the heteropoly salts with one metal atom introduced and one proton left (HMPX) type, (where M = Co, Fe, Mn, and X = W, Mo) with the metal to proton ratio equal one. Among all of the studied catalysts, the highest catalytic activity was observed for HCoPW. The effect indicates that both the acidic and redox properties are required to achieve the best performance. The Baeyer-Villiger (BV) oxidation mechanism proposed identifies the participation of heteropoly compounds in three steps of the investigated reaction: oxidation of aldehyde to peracid (redox function), activation of carbonyl group (Lewis acidity), and decomposition of the Criegee adduct to ?-caprolactone (Brønsted acidity).

| S-EPMC6073195 | biostudies-literature

Catalyst control over regio- and enantioselectivity in Baeyer-Villiger oxidations of functionalized ketones.

Project description:We report a peptide-based catalyst that can strongly influence the regio- and enantioselectivity of the Baeyer-Villiger (BV) oxidation of cyclic ketones bearing amide, urea, or sulfonamide functional groups. Both types of selectivity are thought to arise from a catalyst-substrate hydrogen-bonding interaction. Furthermore, in selected cases, the reactions exhibit the hallmarks of parallel kinetic resolution. The capacity to use catalysis to select between BV products during an asymmetric process may have broad utility for both the synthesis and diversification of complex molecules, including natural products.

| S-EPMC4195385 | biostudies-literature

Identification of the product of toxoflavin lyase: degradation via a Baeyer-Villiger oxidation.

Project description:Toxoflavin (an azapteridine) is degraded to a single product by toxoflavin lyase (TflA) in a reaction dependent on reductant, Mn(II), and oxygen. The isolated product was fully characterized by NMR and MS and was identified as a triazine in which the pyrimidine ring was oxidatively degraded. A mechanism for toxoflavin degradation based on the identification of the enzymatic product and the recently determined crystal structure of toxoflavin lyase is proposed.

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A Synergistic Combinatorial and Chiroptical Study of Peptide Catalysts for Asymmetric Baeyer-Villiger Oxidation.

Project description:We report an approach to the asymmetric Baeyer-Villiger oxidation utilizing bioinformatics-inspired combinatorial screening for catalyst discovery. Scaled-up validation of our on-bead efforts with a circular dichroism-based assay of alcohols derived from the products of solution-phase reactions established the absolute configuration of lactone products; this assay proved equivalent to HPLC in its ability to evaluate catalyst performance, but was far superior in its speed of analysis. Further solution-phase screening of a focused library suggested a mode of asymmetric induction that draws distinct parallels with the mechanism of Baeyer-Villiger monooxygenases.

| S-EPMC4629862 | biostudies-literature

Lipase-mediated Baeyer-Villiger oxidation of benzylcyclopentanones in ester solvents and deep eutectic solvents.

Project description:This work presents the chemo-enzymatic Baeyer-Villiger oxidation of α-benzylcyclopentanones in ester solvents as well as deep eutectic solvents (DES). In the first part of the work the effect of selected reaction conditions on the reaction rate was determined. The oxidation process was most effective in ethyl acetate at 55 °C, with the use of lipase B from Candida antarctica immobilized on acrylic resin and UHP as oxidant. Ultimately, these preliminary studies prompted the development of an effective method for the implementation of lipase-mediated Baeyer-Villiger oxidation of benzylcyclopentanones in DES. The highest conversion was indicated when the oxidizing agent was a component of DESs (minimal DESs). The fastest conversion of ketones to lactones was observed in a mixture of choline chloride with urea hydrogen peroxide. In this case, after 3 days, the conversion of the ketones to lactones products exceeded 92% for all substrates. As a result, two new lactones were obtained and fully characterized by spectroscopic data.

| S-EPMC9427991 | biostudies-literature

A carbonate-forming Baeyer-Villiger monooxygenase.

Project description:Despite the remarkable versatility displayed by flavin-dependent monooxygenases (FMOs) in natural product biosynthesis, one notably missing activity is the oxidative generation of carbonate functional groups. We describe a multifunctional Baeyer-Villiger monooxygenase, CcsB, which catalyzes the formation of an in-line carbonate in the macrocyclic portion of cytochalasin E. This study expands the repertoire of activities of FMOs and provides a possible synthetic strategy for transformation of ketones into carbonates.

| S-EPMC4062580 | biostudies-other

Zr[bis(salicylidene)ethylenediaminato]-mediated Baeyer-Villiger oxidation: stereospecific synthesis of abnormal and normal lactones.

Project description:Baeyer-Villiger oxidation of racemic bicyclic cyclobutanones with Zr[bis(salicylidene)ethylenediaminato] (salen) complex 1 as catalyst in the presence of a urea-hydrogen peroxide adduct was found to proceed enantiospecifically. The enantiotopos selection in the oxidation was governed primarily by the Zr(salen) catalyst, although migratory aptitude (methine > methylene > methyl) in Baeyer-Villiger oxidation affected the selection to a varied extent, depending on the substrate structures; one enantiomer of cyclobutanones gave exclusively a normal lactone expected from the migratory aptitude, and the other enantiomer gave an abnormal lactone preferentially, the formation of which is counter to the migratory aptitude. Furthermore, the rates of abnormal lactone formation were found to be faster than those of normal lactone formation in most of the oxidations examined. For example, the enantiomer of racemic bicyclo[3.2.0]heptan-6-one giving an abnormal lactone reacted 2.2 times faster than the other enantiomer giving a normal lactone. To our knowledge, this example of chemocatalytic Baeyer-Villiger oxidation giving an abnormal lactone in preference to a normal lactone has been previously unreported. This unusual behavior is likely to be attributable to strict control of stereoelectronic demand in Baeyer-Villiger oxidation and chiral recognition by complex 1.

| S-EPMC395977 | biostudies-literature

Chemo-Enzymatic Baeyer-Villiger Oxidation Facilitated with Lipases Immobilized in the Supported Ionic Liquid Phase.

Project description:A novel method for chemo-enzymatic Baeyer-Villiger oxidation of cyclic ketones in the presence of supported ionic liquid-like phase biocatalyst was designed. In this work, multi-walled carbon nanotubes were applied as a support for ionic liquids which were anchored to nanotubes covalently by amide or imine bonds. Next, lipases B from Candida antarctica, Candida rugosa, or Aspergillus oryzae were immobilized on the prepared materials. The biocatalysts were characterized using various techniques, like thermogravimetry, IR spectroscopy, XPS, elemental analysis, and SEM-EDS microscopy. In the proposed approach, a biocatalyst consisting of a lipase as an active phase allowed the generation of peracid in situ from the corresponding precursor and a green oxidant-hydrogen peroxide. The activity and stability of the obtained biocatalysts in the model oxidation of 2-adamantanone were demonstrated. High conversion of substrate (92%) was achieved under favorable conditions (toluene: n-octanoic acid ratio 1:1 = v:v, 35% aq. H2O2 2 eq., 0.080 g of biocatalyst per 1 mmol of ketone at 20 °C, reaction time 4 h) with four reaction cycles without a drop in its activity. Our 'properties-by-design' approach is distinguished by its short reaction time at low temperature and higher thermal stability in comparison with other biocatalysts presented in the literature reports.

| S-EPMC8269471 | biostudies-literature

Microbial-Catalyzed Baeyer-Villiger Oxidation for 3,4-<i>seco</i>-Triterpenoids as Potential HMGB1 Inhibitors.

Project description:Pentacyclic triterpenoids are considered to be the potential HMGB1 inhibitors, but due to the limited number of hydrogen bond donors and the number of rotatable bonds in the rigid skeletons, their further chemical biology research with this target was restricted. To improve these profiles, microbial-catalyzed Baeyer-Villiger oxidation of the primary ursane and oleanane-type triterpenoids including uvaol (1), erythrodiol (2), oleanolic acid (3), and ursolic acid (4) was performed by Streptomyces olivaceus CICC 23628. As a result, ten new and one known A-ring cleaved metabolites were obtained and the possible biogenetic pathways were also discussed based on the HPLC-MS analysis. Furthermore, the direct interactions between compounds 1d, 2b, and HMGB1 were observed by the biolayer interferometry technique. Molecular docking revealed that the newly introduced vicinal diol at C-4, C-24, and the hydroxyl group at C-21 of compound 1d are crucial for binding with HMGB1. The cellular assay showed that co-treatment of 1d could significantly block HMGB1-activated nitric oxide release with an IC50 value of 9.37 μM on RAW 264.7 cells. Altogether, our research provides some insights into 3,4-seco-triterpenes as potential anti-inflammatory candidates for the discovery of novel HMGB1 inhibitors.

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