Browse
Submit Data
Databases
API
Help

Dataset Information

29 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Transformation of alcohols to esters promoted by hydrogen bonds using oxygen as the oxidant under metal-free conditions.

ABSTRACT: One-pot oxidative transformation of alcohols into esters is very attractive, but metal-based catalysts are used in the reported routes. We discovered that the basic ionic liquid 1-ethyl-3-methylimidazolium acetate ([EMIM] OAc) could effectively catalyze this kind of reaction using O₂ as an oxidant without any other catalysts or additives. The oxidative self-esterification of benzylic alcohols or aliphatic alcohols and cross-esterification between benzyl alcohols and aliphatic alcohols could all be achieved with high yields. Detailed study revealed that the cation with acidic proton and basic acetate anion could simultaneously form multiple hydrogen bonds with the hydroxyl groups of the alcohols, which catalyzed the reaction very effectively. As far as we know, this is the first work to carry out this kind of reaction under metal-free conditions.

SUBMITTER: Liu M

PROVIDER: S-EPMC6173529 | biostudies-literature | 2018 Oct

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Transformation of alcohols to esters promoted by hydrogen bonds using oxygen as the oxidant under metal-free conditions.

Liu Mingyang M Zhang Zhanrong Z Liu Huizhen H Xie Zhenbing Z Mei Qingqing Q Han Buxing B

Science advances 20181005 10

One-pot oxidative transformation of alcohols into esters is very attractive, but metal-based catalysts are used in the reported routes. We discovered that the basic ionic liquid 1-ethyl-3-methylimidazolium acetate ([EMIM] OAc) could effectively catalyze this kind of reaction using O<sub>2</sub> as an oxidant without any other catalysts or additives. The oxidative self-esterification of benzylic alcohols or aliphatic alcohols and cross-esterification between benzyl alcohols and aliphatic alcohols ...[more]

PMID: 30310866

Similar Datasets

Base-promoted isomerization of CF3-containing allylic alcohols to the corresponding saturated ketones under metal-free conditions.

Project description:Following to the computational expectation, our previously reported intriguing 1,3-proton shift of 4,4,4-trifluorobut-2-yn-1-ols was successfully extended to the 4,4,4-trifluorobut-2-en-1-ol system under metal-free conditions to afford the corresponding saturated ketones in high to excellent chemical yields using such a convenient and easy-to-handle base as DBU at the toluene refluxing temperature, and utilization of the corresponding optically active substrates unambiguously demonstrated that this transformation proceeded in a highly stereoselective fashion.

| S-EPMC5550803 | biostudies-other

Nature of Alkali- and Coinage-Metal Bonds versus Hydrogen Bonds.

Project description:We have quantum chemically studied the structure and nature of alkali- and coinage-metal bonds (M-bonds) versus that of hydrogen bonds between A-M and B- in archetypal [A-M⋅⋅⋅B]- model systems (A, B=F, Cl and M=H, Li, Na, Cu, Ag, Au), using relativistic density functional theory at ZORA-BP86-D3/TZ2P. We find that coinage-metal bonds are stronger than alkali-metal bonds which are stronger than the corresponding hydrogen bonds. Our main purpose is to understand how and why the structure, stability and nature of such bonds are affected if the monovalent central atom H of hydrogen bonds is replaced by an isoelectronic alkali- or coinage-metal atom. To this end, we have analyzed the bonds between A-M and B- using the activation strain model, quantitative Kohn-Sham molecular orbital (MO) theory, energy decomposition analysis (EDA), and Voronoi deformation density (VDD) analysis of the charge distribution.

| S-EPMC7898866 | biostudies-literature

Transition metal triflate catalyzed conversion of alcohols, ethers and esters to olefins.

Project description:Herein, we report an efficient transition metal triflate catalyzed approach to convert biomass-based compounds, such as monoterpene alcohols, sugar alcohols, octyl acetate and tea tree oil, to their corresponding olefins in high yields. The reaction proceeds through C-O bond cleavage under solvent-free conditions, where the catalytic activity is determined by the oxophilicity and the Lewis acidity of the metal catalyst. In addition, we demonstrate how the oxygen containing functionality affects the formation of the olefins. Furthermore, the robustness of the used metal triflate catalysts, Fe(OTf)3 and Hf(OTf)4, is highlighted by their ability to convert an over 2400-fold excess of 2-octanol to octenes in high isolated yields.

| S-EPMC9080037 | biostudies-literature

NMR reveals hydrogen bonds between oxygen and distal histidines in oxyhemoglobin.

Project description:Compared with free heme, the proteins hemoglobin (Hb) and myoglobin (Mb) exhibit greatly enhanced affinity for oxygen relative to carbon monoxide. This physiologically vital property has been attributed to either steric hindrance of CO or stabilization of O(2) binding by a hydrogen bond with the distal histidine. We report here the first direct evidence of such a hydrogen bond in both alpha- and beta-chains of oxyhemoglobin, as revealed by heteronuclear NMR spectra of chain-selectively labeled samples. Using these spectra, we have assigned the imidazole ring (1)H and (15)N chemical shifts of the proximal and distal histidines in both carbonmonoxy- and oxy-Hb. Because of their proximity to the heme, these chemical shifts are extremely sensitive to the heme pocket conformation. Comparison of the measured chemical shifts with values predicted from x-ray structures suggests differences between the solution and crystal structures of oxy-Hb. The chemical shift discrepancies could be accounted for by very small displacements of the proximal and distal histidines. This suggests that NMR could be used to obtain very high-resolution heme pocket structures of Hb, Mb, and other heme proteins.

| S-EPMC27028 | biostudies-literature

Scalable and Phosphine-Free Conversion of Alcohols to Carbon-Heteroatom Bonds through the Blue Light-Promoted Iodination Reaction.

Project description:One of the fundamental and highly valuable transformations in organic chemistry is the nucleophilic substitution of alcohols. Traditionally, these reactions require strategies that employ stoichiometric hazardous reagents and are associated with difficulty in purification of the by-products. To overcome these challenges, here, we report a simple route toward the diverse conversion of alcohols via an SN2 pathway, in which blue light-promoted iodination is used to form alkyl iodide intermediates from simple unreactive alcohols. The scope of the process tolerates a range of nucleophiles to construct C-N, C-O, C-S, and C-C bonds. Furthermore, we also demonstrate that this method can be used for the preparation and late-stage functionalization of pharmaceuticals, as highlighted by the syntheses of thiocarlide, butoxycaine, and pramoxine.

| S-EPMC7170005 | biostudies-literature

Light-Driven Metal-Free Direct Deoxygenation of Alcohols under Mild Conditions.

Project description:Hydroxyl is widely found in organic molecules as functional group and its deprivation plays an inevitable role in organic synthesis. However, the direct cleavage of Csp3-O bond in alcohols with high selectivity and efficiency, especially without the assistance of metal catalyst, has been a formidable challenge because of its strong bond dissociation energy and unfavorable thermodynamics. Herein, an efficient metal-free strategy that enables direct deoxygenation of alcohols has been developed for the first time, with hydrazine as the reductant induced by light. This protocol features mild reaction conditions, excellent functional group tolerance, and abundant and easily available starting materials, rendering selective deoxygenation of a variety of 1° and 2° alcohols, vicinal diols, and β-1 and even β-O-4 models of natural wood lignin. This strategy is also highlighted by its "traceless" and non-toxic by-products N2 and H2, as readily escapable gases. Mechanistic studies demonstrated dimethyl sulfide being a key intermediate in this transformation.

| S-EPMC7452908 | biostudies-literature

Doping Ruthenium into Metal Matrix for Promoted pH-Universal Hydrogen Evolution.

Project description:For heterogeneous catalysts, the active sites exposed on the surface have been investigated intensively, yet the effect of the subsurface-underlying atoms is much less scrutinized. Here, a surface-engineering strategy to dope Ru into the subsurface/surface of Co matrix is reported, which alters the electronic structure and lattice strain of the catalyst surface. Using hydrogen evolution (HER) as a model reaction, it is found that the subsurface doping Ru can optimize the hydrogen adsorption energy and improve the catalytic performance, with overpotentials of 28 and 45 mV at 10 mA cm-2 in alkaline and acidic media, respectively, and in particular, 28 mV in neutral electrolyte. The experimental results and theoretical calculations indicate that the subsurface/surface doping Ru improves the HER efficiency in terms of both thermodynamics and kinetics. The approach here stands as an effective strategy for catalyst design via subsurface engineering at the atomic level.

| S-EPMC9130909 | biostudies-literature

A facile approach for incorporating tyrosine esters to probe ion-binding sites and backbone hydrogen bonds.

Project description:Amide-to-ester substitutions are used to study the role of the amide bonds of the protein backbone in protein structure, function, and folding. An amber suppressor tRNA/synthetase pair has been reported for incorporation of p-hydroxy-phenyl-L-lactic acid (HPLA), thereby introducing ester substitution at tyrosine residues. However, the application of this approach was limited due to the low yields of the modified proteins and the high cost of HPLA. Here we report the in vivo generation of HPLA from the significantly cheaper phenyl-L-lactic acid. We also construct an optimized plasmid with the HPLA suppressor tRNA/synthetase pair that provides higher yields of the modified proteins. The combination of the new plasmid and the in-situ generation of HPLA provides a facile and economical approach for introducing tyrosine ester substitutions. We demonstrate the utility of this approach by introducing tyrosine ester substitutions into the K+ channel KcsA and the integral membrane enzyme GlpG. We introduce the tyrosine ester in the selectivity filter of the M96V mutant of the KcsA to probe the role of the second ion binding site in the conformation of the selectivity filter and the process of inactivation. We use tyrosine ester substitutions in GlpG to perturb backbone H-bonds to investigate the contribution of these H-bonds to membrane protein stability. We anticipate that the approach developed in this study will facilitate further investigations using tyrosine ester substitutions.

| S-EPMC10790091 | biostudies-literature

Co-N-Si/AC Catalyst for Aerobic Oxidation of Benzyl Alcohols to Esters under Mild Conditions.

Project description:A stable, earth-abundant, reusable cobalt-based heterogeneous catalyst is developed for the oxidative esterification of alcohols under ambient conditions, featuring broad substrate scope, providing good to excellent product yields. This protocol enables easy recyclability of the catalyst, measured up to five times without significant loss of efficiency. The active sites of Co-N-Si/AC are proposed to be Co-N species.

| S-EPMC8622685 | biostudies-literature

Resolution of carboxylic acids using copper(I)-promoted removal of propargylic esters under neutral conditions.

Project description:A method for the optical resolution of carboxylic acids is described. Condensation of racemic carboxylic acids with chiral terminal propargyl alcohols gave separable diastereomeric esters. Chromatographic separation followed by heating the individual diastereomers in methanol with catalytic copper(I) halide regenerated the carboxylic acids in good yields and in enantiomeric ratios of ?94%. This method is particularly useful for the resolution of carboxylic acids that are incompatible with conventional ester hydrolysis.

| S-EPMC3691273 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data