Browse
Submit Data
Databases
API
Help

Dataset Information

27 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Visible-Light Photocatalytic Difluoroalkylation-Induced 1, 2-Heteroarene Migration of Allylic Alcohols in Batch and Flow.

ABSTRACT: A convenient method for the preparation of sp³-rich heterocycles is reported. The method comprises a photocatalytic difluoroalkylation-induced 1,2-heteroarene migration of allylic alcohols. Here we describe for the first time the benefits of using flow to facilitate such migration reactions, including shorter reaction times, higher selectivities, and opportunities to scale the chemistry.

SUBMITTER: Wei XJ

PROVIDER: S-EPMC6154216 | biostudies-literature | 2018 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Visible-Light Photocatalytic Difluoroalkylation-Induced 1, 2-Heteroarene Migration of Allylic Alcohols in Batch and Flow.

Wei Xiao-Jing XJ Noël Timothy T

The Journal of organic chemistry 20180727 18

A convenient method for the preparation of sp<sup>3</sup>-rich heterocycles is reported. The method comprises a photocatalytic difluoroalkylation-induced 1,2-heteroarene migration of allylic alcohols. Here we describe for the first time the benefits of using flow to facilitate such migration reactions, including shorter reaction times, higher selectivities, and opportunities to scale the chemistry. ...[more]

PMID: 30020781

Similar Datasets

Visible-Light Photocatalytic Decarboxylation of ?,?-Unsaturated Carboxylic Acids: Facile Access to Stereoselective Difluoromethylated Styrenes in Batch and Flow.

Project description:The development of synthetic methodologies which provide access to both stereoisomers of ?,?-disubstituted olefins is a challenging undertaking. Herein, we describe the development of an operationally simple and stereoselective synthesis of difluoromethylated styrenes via a visible-light photocatalytic decarboxylation strategy using fac-Ir(ppy)3 as the photocatalyst. Meta- and para-substituted cinnamic acids provide the expected E-isomer. In contrast, ortho-substituted cinnamic acids yield selectively the less stable Z-product, whereas the E-isomer can be obtained via continuous-flow processing through accurate control of the reaction time. Furthermore, our protocol is amenable to the decarboxylative difluoromethylation of aryl propiolic acids.

| S-EPMC5666695 | biostudies-literature

Visible light-mediated difluoroalkylation of electron-deficient alkenes.

Project description:A method for the reductive difluoroalkylation of electron-deficient alkenes using 1,1-difluorinated iodides mediated by irradiation with blue light is described. The reaction involves radical addition of 1,1-difluorinated radicals at the double bond followed by hydrogen atom transfer from sodium cyanoborohydride.

| S-EPMC6036985 | biostudies-literature

Visible-Light-Mediated Selective Arylation of Cysteine in Batch and Flow.

Project description:A mild visible-light-mediated strategy for cysteine arylation is presented. The method relies on the use of eosin Y as a metal-free photocatalyst and aryldiazonium salts as arylating agents. The reaction can be significantly accelerated in a microflow reactor, whilst allowing the in situ formation of the required diazonium salts. The batch and flow protocol described herein can be applied to obtain a broad series of arylated cysteine derivatives and arylated cysteine-containing dipeptides. Moreover, the method was applied to the chemoselective arylation of a model peptide in biocompatible reaction conditions (room temperature, phosphate-buffered saline (PBS) buffer) within a short reaction time.

| S-EPMC5656832 | biostudies-literature

Visible light photoredox-catalyzed deoxygenation of alcohols.

Project description:Carbon-oxygen single bonds are ubiquitous in natural products whereas efficient methods for their reductive defunctionalization are rare. In this work an environmentally benign protocol for the activation of carbon-oxygen single bonds of alcohols towards a reductive bond cleavage under visible light photocatalysis was developed. Alcohols were activated as 3,5-bis(trifluoromethyl)-substituted benzoates and irradiation with blue light in the presence of [Ir(ppy)2(dtb-bpy)](PF6) as visible light photocatalyst and Hünig's base as sacrificial electron donor in an acetonitrile/water mixture generally gave good to excellent yields of the desired defunctionalized compounds. Functional group tolerance is high but the protocol developed is limited to benzylic, α-carbonyl, and α-cyanoalcohols; with other alcohols a slow partial C-F bond reduction in the 3,5-bis(trifluoromethyl)benzoate moiety occurs.

| S-EPMC4168922 | biostudies-literature

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

Visible-Light-Driven Catalytic Deracemization of Secondary Alcohols.

Project description:Deracemization of racemic chiral compounds is an attractive approach in asymmetric synthesis, but its development has been hindered by energetic and kinetic challenges. Here we describe a catalytic deracemization method for secondary benzylic alcohols which are important synthetic intermediates and end products for many industries. Driven by visible light only, this method is based on sequential photochemical dehydrogenation followed by enantioselective thermal hydrogenation. The combination of a heterogeneous dehydrogenation photocatalyst and a chiral molecular hydrogenation catalyst is essential to ensure two distinct pathways for the forward and reverse reactions. These reactions convert a large number of racemic aryl alkyl alcohols into their enantiomerically enriched forms in good yields and enantioselectivities.

| S-EPMC8519112 | biostudies-literature

Visible-light photoredox catalysis in flow.

Project description: Not available

| S-EPMC3496249 | biostudies-literature

Visible-Light Photoredox Catalyzed Dehydrogenative Synthesis of Allylic Carboxylates from Styrenes.

Project description:The visible-light photoredox/[Co(III)] cocatalyzed dehydrogenative functionalization of cyclic and acyclic styryl derivatives with carboxylic acids is documented. The methodology enables the chemo- and regioselective allylic functionalization of styryl compounds, leading to allylic carboxylates (32 examples) under stoichiometric acceptorless conditions. Intermolecular as well as intramolecular variants are documented in high yields (up to 82%). A mechanistic rationale is also proposed on the basis of a combined experimental and spectroscopic investigation.

| S-EPMC8289305 | biostudies-literature

Visible light-induced direct α C-H functionalization of alcohols.

Project description:Considering the synthetic value of introducing active alcoholic hydroxyl group, developing C-H functionalization of alcohols is of significance. Herein, we present a photochemical method that under visible light irradiation, selectfluor can effectively promote the oxidative cross-coupling between alcohols and heteroarenes without the external photocatalysis, achieving the selective α sp3 C-H arylation of alcohol, even in the presence of ether. The N-F activation of selectfluor under blue LEDs irradiation is evidenced by electron paramagnetic resonance (EPR) study, which is the key process for the oxidative activation of α sp3 C-H alcohols. The observed reactivity may have significant implications for chemical transformations.

| S-EPMC6349847 | biostudies-literature

Visible Light-Promoted Oxidative Cross-Coupling of Alcohols to Esters.

Project description:Ester is one of the most significant functional groups in organic chemistry and is enclosed in several valued molecules. Usually, esters are prepared through the acid-catalyzed esterification reaction of carboxylic acids with alcohols, transesterification of esters with alcohols, or via activation of carboxylic acids followed by the addition of alcohols. However, these procedures typically imply the excess use of reactants and harsh reaction conditions. Visible light-mediated photoreactions have been disclosed to display a safe, sustainable, and accessible alternative to traditional methods, and to lead new reactivity modes in organic procedures. In this context, we propose a transition metal-based and organic-based photocatalyst-free synthesis of esters from alcohols induced by visible light. The methodology can be carried out using sunlight or artificial visible light as a solar simulator or a blue LED source.

| S-EPMC10856673 | 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