Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

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

ABSTRACT: 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.

SUBMITTER: Hamada Y

PROVIDER: S-EPMC5550803 | biostudies-other | 2017

REPOSITORIES: biostudies-other

ACCESS DATA

Json Xml

Publications

Base-promoted isomerization of CF<sub>3</sub>-containing allylic alcohols to the corresponding saturated ketones under metal-free conditions.

Hamada Yoko Y Kawasaki-Takasuka Tomoko T Yamazaki Takashi T

Beilstein journal of organic chemistry 20170801

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 t ...[more]

PMID: 28845194

Similar Datasets

One-Pot Conversion of Allylic Alcohols to ?-Methyl Ketones via Iron-Catalyzed Isomerization-Methylation.

Project description:A one-pot iron-catalyzed conversion of allylic alcohols to ?-methyl ketones has been developed. This isomerization-methylation strategy utilized a (cyclopentadienone)iron(0) carbonyl complex as precatalyst and methanol as the C1 source. A diverse range of allylic alcohols undergoes isomerization-methylation to form ?-methyl ketones in good isolated yields (up to 84% isolated yield).

| S-EPMC7007281 | biostudies-literature

Transition Metal Catalyst-Free, Base-Promoted 1,2-Additions of Polyfluorophenylboronates to Aldehydes and Ketones.

Project description:A novel protocol for the transition metal-free 1,2-addition of polyfluoroaryl boronate esters to aldehydes and ketones is reported, which provides secondary alcohols, tertiary alcohols, and ketones. Control experiments and DFT calculations indicate that both the ortho-F substituents on the polyfluorophenyl boronates and the counterion K+ in the carbonate base are critical. The distinguishing features of this procedure include the employment of commercially available starting materials and the broad scope of the reaction with a wide variety of carbonyl compounds giving moderate to excellent yields. Intriguing structural features involving O-H⋅⋅⋅O and O-H⋅⋅⋅N hydrogen bonding, as well as arene-perfluoroarene interactions, in this series of racemic polyfluoroaryl carbinols have also been addressed.

| S-EPMC8362073 | biostudies-literature

Transition-Metal-Free Borylation of Allylic and Propargylic Alcohols.

Project description:The base-catalyzed allylic borylation of tertiary allylic alcohols allows the synthesis of 1,1-disubstituted allyl boronates, in moderate to high yield. The unexpected tandem performance of the Lewis acid-base adduct, [Hbase](+) [MeO-B2 pin2 ](-) favored the formation of 1,2,3-triborylated species from the tertiary allylic alcohols and 1-propargylic cyclohexanol at 90?°C.

| S-EPMC4804746 | biostudies-literature

Triphosgene-amine base promoted chlorination of unactivated aliphatic alcohols.

Project description:Unactivated ?-branched primary and secondary aliphatic alcohols have been successfully transformed into their corresponding alkyl chlorides in high yields upon treatment with a mixture of triphosgene and pyridine in dichloromethane at reflux. These mild chlorination conditions are high yielding, stereospecific, and well tolerated by numerous sensitive functionalities. Furthermore, no nuisance waste products are generated in the course of the reactions.

| S-EPMC4153350 | biostudies-literature

Unsupported Micellar Palladium Nanoparticles for Biphasic Hydrogenation and Isomerization of Hydrophobic Allylic Alcohols in Water.

Project description:This article presents the evaluation of water-soluble palladium nanoparticles with hydrophobic active sites that are ideal for the biphasic colloidal catalysis of water-insoluble organic substrates in aqueous solution. Palladium nanoparticles stabilized with ?-carboxylate-functionalized alkanethiolate are first synthesized using ?-carboxylate-S-alkylthiosulfate as their ligand precursor. The biphasic catalysis is carried out for the reaction of hydrophobic allylic alcohols without using any additional mixing solvent or surfactant, which results in the complete consumption of substrates under the atmospheric pressure of H2 gas and at room temperature in less than 24 h. Systematic investigations on the influence of pH and substrate size are also performed to examine the utility of these thiolate-capped palladium nanoparticles as structurally stable and water-soluble micellar catalysts for the biphasic reaction.

| S-EPMC5450820 | biostudies-literature

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

Project description: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.

| S-EPMC6173529 | biostudies-literature

Base Metal-Catalyzed Direct Olefinations of Alcohols with Sulfones.

Project description:Herein, a base-metal nickel-catalyzed direct olefination of alcohols with sulfones is reported. The reaction operates under low catalyst loading and does not require an external redox reagent. A wide range of trans-stilbenes and styrenes were synthesized in good yields and selectivities. Biologically active stilbene DMU-212 could also be synthesized in a single step under these conditions. Mechanistic studies involving kinetic isotope effect, deuterium labeling experiments, and catalytic and stoichiometric reactions with possible catalytic intermediates were performed to elucidate a plausible mechanism.

| S-EPMC6648817 | biostudies-literature

Base-Promoted C-C Bond Activation Enables Radical Allylation with Homoallylic Alcohols.

Project description:The Cα-Cβ bond in homoallylic alcohols can be activated under basic conditions, qualifying these nonstrained acyclic systems as radical allylation reagents. This reactivity is exemplified by photoinitiated (with visible light and/or blue LEDs) allylation of perfluoroalkyl and alkyl radicals generated from perfluoroalkyl iodides and alkylpyridinium salts, respectively, with homoallylic alcohols. C-radical addition to the double bond of the title reagents and subsequent base-promoted homolytic Cα-Cβ cleavage leads to the formation of the corresponding allylated products along with ketyl radicals that act as single electron reductants to sustain the chain reactions. Substrate scope is documented and the role of base in the C-C bond activation is studied by computation.

| S-EPMC7021447 | biostudies-literature

Manganese-Catalyzed Hydrogenation of Ketones under Mild and Base-free Conditions.

Project description:In this paper, several Mn(I) complexes were applied as catalysts for the homogeneous hydrogenation of ketones. The most active precatalyst is the bench-stable alkyl bisphosphine Mn(I) complex fac-[Mn(dippe) (CO)3(CH2CH2CH3)]. The reaction proceeds at room temperature under base-free conditions with a catalyst loading of 3 mol % and a hydrogen pressure of 10 bar. A temperature-dependent selectivity for the reduction of α,β-unsaturated carbonyls was observed. At room temperature, the carbonyl group was selectively hydrogenated, while the C=C bond stayed intact. At 60 °C, fully saturated systems were obtained. A plausible mechanism based on DFT calculations which involves an inner-sphere hydride transfer is proposed.

| S-EPMC8155567 | biostudies-literature

Enantioselective dichlorination of allylic alcohols.

Project description:The development of an enantioselective allylic alcohol dichlorination catalyzed by dimeric cinchona alkaloid derivatives and employing aryl iododichlorides as chlorine sources is reported. Reaction optimization, exploration of the substrate scope, and a model for stereoinduction are presented.

| S-EPMC3107004 | 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