Browse
Submit Data
Databases
API
Help

Dataset Information

20 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Synthesis of Benzylic Alcohols by C-H Oxidation.

ABSTRACT: Selective methylene C-H oxidation for the synthesis of alcohols with a broad scope and functional group tolerance is challenging due to the high proclivity for further oxidation of alcohols to ketones. Here, we report the selective synthesis of benzylic alcohols employing bis(methanesulfonyl) peroxide as an oxidant. We attempt to provide a rationale for the selectivity for monooxygenation, which is distinct from previous work; a proton-coupled electron transfer mechanism (PCET) may account for the difference in reactivity. We envision that our method will be useful for applications in the discovery of drugs and agrochemicals.

SUBMITTER: Tanwar L

PROVIDER: S-EPMC6863597 | biostudies-literature | 2019 Nov

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Synthesis of Benzylic Alcohols by C-H Oxidation.

Tanwar Lalita L Börgel Jonas J Ritter Tobias T

Journal of the American Chemical Society 20191105 45

Selective methylene C-H oxidation for the synthesis of alcohols with a broad scope and functional group tolerance is challenging due to the high proclivity for further oxidation of alcohols to ketones. Here, we report the selective synthesis of benzylic alcohols employing bis(methanesulfonyl) peroxide as an oxidant. We attempt to provide a rationale for the selectivity for monooxygenation, which is distinct from previous work; a proton-coupled electron transfer mechanism (PCET) may account for t ...[more]

PMID: 31689095

Similar Datasets

Asymmetric synthesis of tertiary benzylic alcohols.

Project description:Vinyl, aryl, and alkynyl organometallics add to ketones containing a stereogenic sulfoxide. Tertiary alcohols are generated in diastereomerically and enantiomerically pure form. Reductive lithiation converts the sulfoxide into a variety of useful functional groups.

| S-EPMC3028934 | biostudies-literature

Cerium-photocatalyzed aerobic oxidation of benzylic alcohols to aldehydes and ketones.

Project description:We have developed a cerium-photocatalyzed aerobic oxidation of primary and secondary benzylic alcohols to aldehydes and ketones using inexpensive CeCl3·7H2O as photocatalyst and air oxygen as the terminal oxidant.

| S-EPMC8313980 | biostudies-literature

Green, Palladium-Catalyzed Synthesis of Benzylic H-phosphinates from Hypophosphorous Acid and Benzylic Alcohols.

Project description:Benzylic alcohols cross-couple directly with concentrated H(3)PO(2) using Pd/xantphos (1 or 2 mol-%). Depending on the substrate, DMF at 110°C, or t-AmOH at reflux with a Dean-Stark trap, can be used. A broad range of benzylic alcohols reacted successfully in moderate to good yields. The preparation of other organophosphorus compounds (phosphinic and phosphonic acids) is also demonstrated.Asymmetric reaction with (R)-1-(2-naphthyl)ethanol provided the corresponding H-phosphinic acid in 77% ee. The methodology provides a green, PCl(3)-free, entry into benzylic-H-phosphinic acids.

| S-EPMC3551600 | biostudies-literature

Sodium Copper Chlorophyllin Catalyzed Chemoselective Oxidation of Benzylic Alcohols and Diarylmethanes in Water.

Project description:We report the highly efficient and chemoselective oxidation of benzylic alcohols catalyzed by sodium copper chlorophyllin in water, producing corresponding arylcarbonyl compounds. Importantly, the catalytic system exhibits a wide substrate scope and high functional group tolerance. Moreover, secondary alcohols and even diarylmethanes were smoothly oxidized to the desired aryl ketones with excellent yields.

| S-EPMC6222594 | biostudies-literature

Direct Synthesis of Secondary Benzylic Alcohols Enabled by Photoredox/Ni Dual-Catalyzed Cross-Coupling.

Project description:An operationally simple, mild, redox-neutral method for the cross-coupling of α-hydroxyalkyltrifluoroborates is reported. Utilizing an Ir photocatalyst, α-hydroxyalkyl radicals are generated from the single-electron oxidation of the trifluoroborates, and these radicals are subsequently engaged in a nickel-catalyzed C-C bond-forming reaction with aryl halides. The process is highly selective, functional group tolerant, and step economical, which allows the direct synthesis of secondary benzylic alcohol motifs.

| S-EPMC5732067 | biostudies-literature

Selective oxidation of benzylic and allylic alcohols using Mn(OAc)3/catalytic 2,3-dichloro-5,6-dicyano-1,4-benzoquinone.

Project description:A practical, chemoselective oxidation of alcohols employing catalytic quantities of DDQ as the oxidant and Mn(OAc)(3) as the co-oxidant is described. Electron-rich benzylic alcohols are oxidized efficiently to their corresponding carbonyls, but less electron-rich benzylic alcohols remain unchanged. Allylic alcohols are rapidly oxidized to their corresponding aldehyde or ketone counterparts in high yields. This protocol is operationally simple, employs an inexpensive source of Mn(OAc)(3), has short reaction times, and exhibits a significant chemoselectivity favoring allylic alcohols over benzylic alcohols. This procedure also avoids the use of very large excesses of reagents and sometimes poor reproducibility that characterize previously developed reagents such as MnO(2).

| S-EPMC4482348 | biostudies-literature

Triflimide-catalyzed allylsilane annulations of benzylic alcohols for the divergent synthesis of indanes and tetralins.

Project description:The development of a triflimide-catalyzed annulation of benzylic alcohols with allylsilanes for the synthesis of indane or tetralin structures is reported. In this fragment coupling reaction, complexity is built rapidly from readily available starting materials to yield diverse sets of products with up to three contiguous stereocenters. Indanes or tetralins can be generated from common precursors depending on the structure of the allylsilane reagent used. The concise synthesis of several lignan natural products highlights the utility of this newly devised methodology.

| S-EPMC5407261 | biostudies-other

Visible-Light Photoredox-Catalyzed Amidation of Benzylic Alcohols.

Project description:A new photocatalyzed route to amides from alcohols and amines mediated by visible light is presented. The reaction is carried out in ethyl acetate as a solvent. Ethyl acetate can be defined a green and bio-based solvent. The starting materials such as the energy source are easily available, stable, and inexpensive. The reaction has shown to be general and high yielding.

| S-EPMC8009506 | biostudies-literature

Catalytic Enantioselective Carbon-Oxygen Bond Formation: Phosphine-Catalyzed Synthesis of Benzylic Ethers via the Oxidation of Benzylic C-H Bonds.

Project description:Benzylic alcohols and ethers are common subunits in bioactive molecules, as well as useful intermediates in organic chemistry. In this Communication, we describe a new approach to the enantioselective synthesis of benzylic ethers through the chiral phosphine-catalyzed coupling of two readily available partners, ?-aryl-substituted alkynoates and alcohols, under mild conditions. In this process, the alkynoate partner undergoes an internal redox reaction. Specifically, the benzylic position is oxidized with good enantioselectivity, and the alkyne is reduced to the alkene.

| S-EPMC5065328 | biostudies-literature

Direct conversion of benzylic and allylic alcohols to phosphonates.

Project description:Benzyl phosphonate esters often serve as reagents in Horner-Wadsworth-Emmons reactions. In most cases, they can be prepared from benzylic alcohols via formation of the corresponding halide followed by an Arbuzov reaction. To identify a more direct synthesis of phosphonate esters, we have developed a one-flask procedure for conversion of benzylic and allylic alcohols to the corresponding phosphonates through treatment with triethyl phosphite and ZnI(2).

| S-EPMC3204863 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

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