Browse
Submit Data
Databases
API
Help

Dataset Information

22 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Catalytic Hydrothiolation: Regio- and Enantioselective Coupling of Thiols and Dienes.

ABSTRACT: We report a Rh-catalyzed hydrothiolation of 1,3-dienes, including petroleum feedstocks. Either secondary or tertiary allylic sulfides can be generated from the selective addition of a thiol to the more substituted double bond of a diene. The catalyst tolerates a wide range of functional groups, and the loading can be as low as 0.1 mol %.

SUBMITTER: Yang XH

PROVIDER: S-EPMC6563822 | biostudies-literature | 2018 Aug

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Catalytic Hydrothiolation: Regio- and Enantioselective Coupling of Thiols and Dienes.

Yang Xiao-Hui XH Davison Ryan T RT Dong Vy M VM

Journal of the American Chemical Society 20180809 33

We report a Rh-catalyzed hydrothiolation of 1,3-dienes, including petroleum feedstocks. Either secondary or tertiary allylic sulfides can be generated from the selective addition of a thiol to the more substituted double bond of a diene. The catalyst tolerates a wide range of functional groups, and the loading can be as low as 0.1 mol %. ...[more]

PMID: 30091909

Similar Datasets

Regio- and enantioselective catalytic monoepoxidation of conjugated dienes: synthesis of chiral allylic cis-epoxides.

Project description:Ti(IV)-salan 4 catalyzes the diastereo- and enantioselective monoepoxidation of conjugated dienes using 30% H2O2 at rt or below even in the presence of other olefins and adjacent stereocenters. Its enantiomer, ent-4, provides access to the opposite diastereomer or enantiomer. The resultant chiral allylic epoxides, and the triols derived from them, are versatile synthetic intermediates as well as substructures present in many bioactive natural products. The epoxidation is highly specific for Z-olefins. For 1-acyl(silyl)oxypenta-2,4-dienes, epoxidation of the distal olefin is generally favored in contrast to the adjacent regioselectivity characteristic of Sharpless, peracid, and other directed epoxidations of hydroxylated dienes.

| S-EPMC4342986 | biostudies-literature

Enantioselective Coupling of Dienes and Phosphine Oxides.

Project description:We report a Pd-catalyzed intermolecular hydrophosphinylation of 1,3-dienes to afford chiral allylic phosphine oxides. Commodity dienes and air stable phosphine oxides couple to generate organophosphorus building blocks with high enantio- and regiocontrol. This method constitutes the first asymmetric hydrophosphinylation of dienes.

| S-EPMC6607437 | biostudies-literature

Regio- and enantioselective hydroamination of dienes by gold(I)/menthol cooperative catalysis.

Project description:Alcohol is key: regio- and enantioselective hydroamination of 1,3-dienes has been achieved with the dinuclear catalyst (R)-DTBM-SEGPHOS. The rate and selectivity of the reaction are enhanced by alcohol additives like menthol, which coordinates the cationic gold(I) to generate a Brønsted acid that can participate in catalysis. Mbs=p-methoxybenzenesulfonyl.

| S-EPMC3382038 | biostudies-literature

Highly Regio- and Stereoselective Catalytic Synthesis of Conjugated Dienes and Polyenes.

Project description:Conjugated dienes and polyenes are typically synthesized by sequential introduction of C?C bonds. Here, we report a practical and scalable, catalytic dienylation that is highly regio- and stereoselective for both C?C bonds. The reaction is enabled by a stereoselective palladium-catalyzed cross-coupling that is preceded by a regioselective base-induced ring opening of readily available sulfolenes. The dienylation reaction is particularly useful for the synthesis of synthetically challenging dienes containing cis double bonds. We also show that the reaction can serve as a synthetic platform for the construction of conjugated polyenes.

| S-EPMC6171353 | biostudies-literature

Catalytic Regio- and Enantioselective Haloazidation of Allylic Alcohols.

Project description:Herein we report a highly regio- and stereoselective haloazidation of allylic alcohols. This enantioselective reaction uses readily available materials and can be performed on a variety of alkyl-substituted alkenes and can incorporate either bromine or chlorine as the electrophilic halogen component. Both halide and azido groups of the resulting products can be transformed into valuable building blocks with complete stereospecificity. The first example of an enantioselective 1,4-haloazidation of a conjugated diene is reported as well as its application to a concise synthesis of an aza-sugar.

| S-EPMC6499076 | biostudies-literature

Catalytic Enantioselective Hetero-dimerization of Acrylates and 1,3-Dienes.

Project description:1,3-Dienes are ubiquitous and easily synthesized starting materials for organic synthesis, and alkyl acrylates are among the most abundant and cheapest feedstock carbon sources. A practical, highly enantioselective union of these two readily available precursors giving valuable, enantio-pure skipped 1,4-diene esters (with two configurationally defined double bonds) is reported. The process uses commercially available cobalt salts and chiral ligands. As illustrated by the use of 20 different substrates, including 17 prochiral 1,3-dienes and 3 acrylates, this hetero-dimerization reaction is tolerant of a number of common organic functional groups (e.g., aromatic substituents, halides, isolated mono- and di-substituted double bonds, esters, silyl ethers, and silyl enol ethers). The novel results including ligand, counterion, and solvent effects uncovered during the course of these investigations show a unique role of a possible cationic Co(I) intermediate in these reactions. The rational evolution of a mechanism-based strategy that led to the eventual successful outcome and the attendant support studies may have further implications for the expanding use of low-valent group 9 metal complexes in organic synthesis.

| S-EPMC5729116 | biostudies-literature

Rhodium-Catalyzed Hydrofunctionalization: Enantioselective Coupling of Indolines and 1,3-Dienes.

Project description:We communicate a strategy for the hydrofunctionalization of 1,3-dienes via Rh-hydride catalysis. Conjugated dienes are coupled to nucleophiles to demonstrate the feasibility of novel C-C, C-O, C-S, and C-N bond forming processes. In the presence of a chiral JoSPOphos ligand, hydroamination generates chiral allylic amines with high regio- and enantioselectivity. Tuning both the pKa and steric properties of an acid-additive is critical for enantiocontrol.

| S-EPMC6857534 | biostudies-literature

Asymmetric 1,4-dihydroxylation of 1,3-dienes by catalytic enantioselective diboration.

Project description:Asymmetric 1,4-dihydroxylations of 1,3-dienes, and other transformations, are initiated by the Pt-catalyzed enantioselective addition of bis(pinacolato)diboron (B(2)(pin)(2)) to conjugated dienes. The studies reported in this communication suggest that both cyclic and acyclic substrates will participate in this reaction; however, dienes which are unable to adopt the S-cis conformation are unreactive. For most substrates, 1,4-addition is the predominant pathway. In addition to oxidation to the derived 2-buten-1,4-diol, stereoselective carbonyl allylation with the intermediate bis(boronate) ester is also described.

| S-EPMC2747290 | biostudies-literature

Catalytic enantioselective formation of chiral-bridged dienes which are themselves ligands for enantioselective catalysis.

Project description:This paper reports a method for highly enantioselective Diels-Alder reaction with an acetylene equivalent to produce chiral-bridged dienes. These dienes, by coordination to Rh(I), can serve as catalysts for the enantioselective addition of vinyl or aryl groups to alpha,beta-unsaturated ketones.

| S-EPMC2814301 | biostudies-literature

Catalytic Hydrothiolation: Counterion-Controlled Regioselectivity.

Project description:In this Article, we expand upon the catalytic hydrothiolation of 1,3-dienes to afford either allylic or homoallylic sulfides with high regiocontrol. Mechanistic studies support a pathway in which regioselectivity is dictated by the choice of counterion associated with the Rh center. Non-coordinating counterions, such as SbF6-, allow for η4-diene coordination to Rh complexes and result in allylic sulfides. In contrast, coordinating counterions, such as Cl-, favor neutral Rh complexes in which the diene binds η2 to afford homoallylic sulfides. We propose mechanisms that rationalize a fractional dependence on thiol for the 1,2-Markovnikov hydrothiolation while accounting for an inverse dependence on thiol in the 3,4- anti-Markovnikov pathway. Through the hydrothiolation of an essential oil (β-farnesene), we achieve the first enantioselective synthesis of (-)-agelasidine A.

| S-EPMC6563821 | 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