Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Ir(iii)-catalyzed thioether directed arene C-H alkenylation.

ABSTRACT: In this study, we demonstrate an Ir(iii)-catalyzed thioether directed alkenylation of arene C-H bonds under mild reaction conditions. The selectivity for mono- or di-alkenylation is controlled by the concentration of alkene and oxidant loading. Various functional groups are tolerated, and moderate to good yields of alkenylated products are achieved.

SUBMITTER: Li C

PROVIDER: S-EPMC9072104 | biostudies-literature | 2019 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Ir(iii)-catalyzed thioether directed arene C-H alkenylation.

Li Chen C Chen Xian X Bao Rui-Peng RP Li Dong-Li DL Zhang Kun K Wang Dong-Hui DH

RSC advances 20190924 52

In this study, we demonstrate an Ir(iii)-catalyzed thioether directed alkenylation of arene C-H bonds under mild reaction conditions. The selectivity for mono- or di-alkenylation is controlled by the concentration of alkene and oxidant loading. Various functional groups are tolerated, and moderate to good yields of alkenylated products are achieved. ...[more]

PMID: 35530243

Similar Datasets

Highly Anti-Markovnikov Selective Oxidative Arene Alkenylation Using Ir(I) Catalyst Precursors and Cu(II) Carboxylates.

Project description:The Ir(I) complex [Ir(μ-Cl)(coe)2]2 (coe = cis-cyclooctene) is a catalyst precursor for benzene alkenylation using Cu(II) carboxylate salts. Using [Ir(μ-Cl)(coe)2]2, propenylbenzenes are formed from the reaction of benzene, propylene, and CuX2 (X = acetate, pivalate, or 2-ethylhexanoate). The Ir-catalyzed reactions selectively produce anti-Markovnikov products, trans-β-methylstyrene, cis-β-methylstyrene, and allylbenzene, along with minor amounts of the Markovnikov product, α-methylstyrene. The selectivity for the anti-Markovnikov products changed as the reaction progressed. For example, in a reaction that uses 240 equiv of Cu(OHex)2 (related to Ir), the selectivity for the anti-Markovnikov products increases from 18:1 at 3 h to 42:1 at 42 h with 30 psig of propylene at 150 °C. Studies of product stability have revealed that the increase in the selectivity for anti-Markovnikov products is not the result of an isomerization process or the selective decomposition of specific products. Rather, the change in selectivity correlates with the ratio of Cu(II) to Cu(I) in the solution, which decreases as the reaction progresses. We propose that the identity of the active catalyst changes as Cu(I) is accumulated, resulting in the formation of an active catalyst that is more selective for anti-Markovnikov products. Using a 4:1 Cu(I)/Cu(II) ratio at the start of the reaction, a 65(3):1 anti-Markovnikov/Markovnikov ratio is observed.

| S-EPMC11005047 | biostudies-literature

Cobalt-catalyzed, aminoquinoline-directed C(sp²)-H bond alkenylation by alkynes.

Project description:A method for cobalt-catalyzed, aminoquinoline- and picolinamide-directed C(sp(2))-H bond alkenylation by alkynes was developed. The method shows excellent functional-group tolerance and both internal and terminal alkynes are competent substrates for the coupling. The reaction employs a Co(OAc)2?4?H2O catalyst, Mn(OAc)2 co-catalyst, and oxygen (from air) as a terminal oxidant.

| S-EPMC4167400 | biostudies-literature

Ir-catalyzed enantioselective B-H alkenylation for asymmetric synthesis of chiral-at-cage o‑carboranes.

Project description:The asymmetric synthesis of chiral-at-cage o-carboranes, whose chirality is associated with the substitution patterns on the polyhedron, is of great interest as the icosahedral carboranes have wide applications in medicinal and materials chemistry. Herein we report an intermolecular Ir-catalyzed enantioselective B-H alkenylation for efficient and facile synthesis of chiral-at-cage o-carboranes with new skeletons under mild reaction conditions. Generally very good to excellent yields with up to 99% ee can be achieved in this Ir-catalyzed B-H alkenylation. The enantiocontrol model is proposed based on Density Functional Theory calculations in which the use of chiral phosphoramidite ligand is essential for such asymmetric o-carborane B-H alkenylation.

| S-EPMC8654863 | biostudies-literature

Cobalt-catalyzed directed C-H alkenylation of pivalophenone N-H imine with alkenyl phosphates.

Project description:A cobalt-N-heterocyclic carbene (NHC) catalyst efficiently promotes an ortho C-H alkenylation reaction of pivalophenone N-H imine with an alkenyl phosphate. The reaction tolerates various substituted pivalophenone N-H imines as well as cyclic and acyclic alkenyl phosphates.

| S-EPMC5905286 | biostudies-literature

Iridium-catalyzed arene ortho-silylation by formal hydroxyl-directed C-H activation.

Project description:A strategy for the ortho-silylation of aryl ketone, benzaldehyde, and benzyl alcohol derivatives has been developed in which a hydroxyl group formally serves as the directing element for Ir-catalyzed arene C-H bond activation. One-pot generation of a (hydrido)silyl ether from the carbonyl compound or alcohol is followed by dehydrogenative cyclization at 80-100 °C in the presence of norbornene as a hydrogen acceptor and the combination of 1 mol % [Ir(cod)OMe]2 and 1,10-phenanthroline as a catalyst to form benzoxasiloles. The synthetic utility of the benzoxasilole products is demonstrated by conversion to phenol or biaryl derivatives by Tamao-Fleming oxidation or Hiyama cross-coupling. Both of these transformations of the C-H silylation products exploit the Si-O bond in the system and proceed by activation of the silyl moiety with hydroxide, rather than fluoride.

| S-EPMC3135680 | biostudies-literature

Photoredox-Catalyzed Alkenylation of Benzylsulfonium Salts.

Project description:Visible light-mediated radical alkenylation of benzylsulfonium salts was achieved by means of fac-Ir(ppy)3 as a photocatalyst, giving allylbenzenes as products. A variety of functional groups, such as halogen, ester, and cyano, were well tolerated in this transformation. Starting benzylsulfonium salts could be readily prepared from benzyl alcohols by an acid-mediated substitution, increasing the synthetic utility of this transformation.

| S-EPMC6442929 | biostudies-literature

Proton-catalyzed hydrogenation of a d(8) Ir(I) complex yields a trans Ir(III) dihydride.

Project description:Hydrogenation of the (PONOP)Ir(I)CH(3) complex [PONOP = 2,6-bis(di-tert-butylphosphinito)pyridine] yields the unexpected trans-dihydride species (PONOP)IrCH(3)(H)(2). Mechanistic investigations have revealed that this reaction proceeds via proton-catalyzed H(2) cleavage, a pathway that circumvents the intermediacy of the typically invoked cis-dihydride isomer. Protonation yields the cationic (PONOP)Ir(CH(3))(H)(+) complex, which is then trapped by H(2) to yield an eta(2)-H(2) complex. Deprotonation of this species yields the trans-dihydride. Intermediates in the proposed pathway have been confirmed by independent low-temperature syntheses and spectroscopic observations.

| S-EPMC2858392 | biostudies-literature

Palladium-catalyzed enantioselective alkenylation of alkenylbenzene derivatives.

Project description:A regioselective and enantioselective palladium-catalyzed relay Heck alkenylation of alkenylbenzene derivatives to construct remote stereocenters is disclosed. Various β-substituted styrenes were readily obtained in moderate yields with good to excellent levels of enantioselectivity. This strategy provides rapid access to enantioenriched δ, ε, ζ, and η-alkenyl aryl compounds from simple starting materials. Mechanistic studies suggest that termination of the relay reaction is controlled by affinity of the arene for the Pd complex during migration.

| S-EPMC6685350 | biostudies-literature

Copper-catalyzed <i>O</i>-alkenylation of phosphonates.

Project description:Copper catalysis allows the direct oxygen alkenylation of dialkyl phosphonates with alkenyl(aryl)iodonium salts with selective transfer of the alkenyl group. This novel methodology proceeds with a wide range of phosphonates under mild conditions and gives straightforward access to valuable enol phosphonates in very good yields.

| S-EPMC7136550 | biostudies-literature

Ir(III)-Catalyzed Carbocarbation of Alkynes through Undirected Double C-H Bond Activation of Anisoles.

Project description:A novel, electron-deficient cyclopentadienyl iridium(III) catalyst enables sequential cleavage of arene C(sp2)-H and methoxy C(sp3)-H bonds of anisoles, generating reactive metalacycles that insert difluoroalkynes to afford chromenes under mild reaction conditions. This transformation is an arylalkylation of an alkyne-a carbocarbation-via a nonchelate-assisted cleavage of two C-H bonds.

| S-EPMC5972829 | 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