Browse
Submit Data
Databases
API
Help

Dataset Information

30 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Visible Light-Induced Room-Temperature Heck Reaction of Functionalized Alkyl Halides with Vinyl Arenes/Heteroarenes.

ABSTRACT: The first visible light-induced Pd-catalyzed Heck reaction of ?-heteroatom substituted alkyl iodides and -bromides with vinyl arenes/heteroarenes has been developed. This transformation efficiently proceeds at room temperature and enables synthesis of valuable functionalized allylic systems, such as allylic silanes, boronates, germanes, stannanes, pivalates, phosphonates, phthalimides, and tosylates from the corresponding ?-substituted methyl iodides. Notably, synthesis of the latter substrates failed under existing thermally induced Pd-catalyzed conditions, which highlights the importance of visible light for this transformation.

SUBMITTER: Kurandina D

PROVIDER: S-EPMC5728111 | biostudies-literature | 2017 Nov

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Visible Light-Induced Room-Temperature Heck Reaction of Functionalized Alkyl Halides with Vinyl Arenes/Heteroarenes.

Kurandina Daria D Parasram Marvin M Gevorgyan Vladimir V

Angewandte Chemie (International ed. in English) 20171009 45

The first visible light-induced Pd-catalyzed Heck reaction of α-heteroatom substituted alkyl iodides and -bromides with vinyl arenes/heteroarenes has been developed. This transformation efficiently proceeds at room temperature and enables synthesis of valuable functionalized allylic systems, such as allylic silanes, boronates, germanes, stannanes, pivalates, phosphonates, phthalimides, and tosylates from the corresponding α-substituted methyl iodides. Notably, synthesis of the latter substrates ...[more]

PMID: 28941019

Similar Datasets

Heck Reaction of Electronically Diverse Tertiary Alkyl Halides.

Project description:The efficient Pd-catalyzed Heck reaction of diverse tertiary alkyl halides with alkenes has been developed. Unactivated tertiary alkyl halides efficiently react at room temperature under visible light irradiation with no exogenous photosensitizers required. For activated tertiary alkyl halides, the same catalytic system works well without light. These methods offer a general access to electronically diverse alkenes possessing quaternary and functionalized tertiary allylic carbon centers. The substituents at these centers include alkyl-, carbalkoxy-, tosyl-, phosphonyl-, and boronate groups. It was also shown that the end-game mechanism of this transformation may vary depending on the type of the substrates used.

| S-EPMC5813498 | biostudies-literature

Dehalogenation of Functionalized Alkyl Halides in Water at Room Temperature.

Project description:Alkyl bromides and chlorides can be reduced to the corresponding hydrocarbons utilizing zinc in the presence of an amine additive. The process takes place in water at ambient temperatures, enabled by a commercially available designer surfactant. The reaction medium can be readily recycled, and the amount of organic solvent invested for product isolation is minimal, leading to very low E Factors.

| S-EPMC4267473 | biostudies-literature

Cross-Electrophile Coupling of Vinyl Halides with Alkyl Halides.

Project description:An improved method for the reductive coupling of aryl and vinyl bromides with alkyl halides that gave high yields for a variety of substrates at room temperature with a low (2.5 to 0.5?mol?%) catalyst loading is presented. Under the optimized conditions, difficult substrates, such as unhindered alkenyl bromides, can be coupled to give the desired olefins with minimal diene formation and good stereoretention. These improved conditions also worked well for aryl bromides. For example, a gram-scale reaction was demonstrated with 0.5?mol?% catalyst loading, whereas reactions at 10?mol?% catalyst loading completed in as little as 20?minutes. Finally, a low-cost single-component pre-catalyst, (bpy)NiI2 (bpy=2,2'-bipyridine) that is both air- and moisture-stable over a period of months was introduced.

| S-EPMC4973476 | biostudies-literature

Copper-catalyzed oxidative Heck reactions between alkyltrifluoroborates and vinyl arenes.

Project description:We report herein that potassium alkyltrifluoroborates can be utilized in oxidative Heck-type reactions with vinyl arenes. The reaction is catalyzed by a Cu(OTf)2/1,10-phenanthroline with MnO2 as the stoichiometric oxidant. In addition to the alkyl Heck, amination, esterification, and dimerization reactions of alkyltrifluoroborates are demonstrated under analogous reaction conditions. Evidence for an alkyl radical intermediate is presented.

| S-EPMC3978782 | biostudies-literature

HOTf-Catalyzed Alkyl-Heck-type Reaction.

Project description:The Heck reaction, along with other cross-coupling reactions, led to a revolution in organic chemistry. In the last 50 years, metal-catalyzed, photo-induced, or base-mediated Heck and Heck-type reactions have been elegantly developed. Brønsted acid-catalyzed Heck (or Heck-type) reactions are still unknown, however. By introducing alkyl peroxides as the key intermediates, primary, secondary, and tertiary aliphatic carboxylic acids are therefore applied here in a one-pot Brønsted acid-catalyzed Heck-type reaction, to deliver E-alkenes exclusively in most cases. The use of HOTf is vital to the reaction, whose mechanism is supported by both experimental and computational results. This method can be expanded to the direct alkylation of complex natural products.

| S-EPMC6137405 | biostudies-literature

N-Acyloxyphthalimides as nitrogen radical precursors in the visible light photocatalyzed room temperature C-H amination of arenes and heteroarenes.

Project description:This paper reports a room temperature visible light photocatalyzed method for the C-H amination of arenes and heteroarenes. A key enabling advance in this work is the design of N-acyloxyphthalimides as precursors to nitrogen-based radical intermediates for these transformations. A broad substrate scope is presented, including the selective meta-amination of pyridine derivatives. A radical aromatic substitution mechanism is proposed.

| S-EPMC4004272 | biostudies-literature

Visible-light-mediated Minisci C-H alkylation of heteroarenes with unactivated alkyl halides using O<sub>2</sub> as an oxidant.

Project description:Herein, we report a protocol for direct visible-light-mediated Minisci C-H alkylation of heteroarenes with unactivated alkyl halides using molecular oxygen as an oxidant at room temperature. This mild protocol is compatible with a wide array of sensitive functional groups and has a broad substrate scope. Notably, functionalization of (iso)quinolines, pyridines, phenanthrolines, quinazoline, and other heterocyclic compounds with unactivated primary, secondary, and tertiary alkyl halides proceeds smoothly under the standard conditions. The robustness of this protocol is further demonstrated by the late-stage functionalization of complex nitrogen-containing natural products and drugs.

| S-EPMC6349069 | biostudies-literature

General electrochemical Minisci alkylation of <i>N</i>-heteroarenes with alkyl halides.

Project description:Herein, we report, a general, facile and environmentally friendly Minisci-type alkylation of N-heteroarenes under simple and straightforward electrochemical conditions using widely available alkyl halides as radical precursors. Primary, secondary and tertiary alkyl radicals have been shown to be efficiently generated and coupled with a large variety of N-heteroarenes. The method presents a very high functional group tolerance, including various heterocyclic-based natural products, which highlights the robustness of the methodology. This applicability has been further proved in the synthesis of various interesting biologically valuable building blocks. In addition, we have proposed a mechanism based on different proofs and pieces of electrochemical evidence.

| S-EPMC9172443 | biostudies-literature

Visible Light Induced Bronsted Acid Assisted Pd-Catalyzed Alkyl Heck Reaction of Diazo Compounds and N-Tosylhydrazones.

Project description:A mild visible light-induced palladium-catalyzed alkyl Heck reaction of diazo compounds and N-tosylhydrazones is reported. A broad range of vinyl arenes and heteroarenes with high functional group tolerance, as well as a range of different diazo compounds, can efficiently undergo this transformation. This method features Brønsted acid-assisted generation of hybrid palladium C(sp3 )-centered radical intermediate, which allowed for new selective C-H functionalization protocol.

| S-EPMC8712420 | biostudies-literature

Practical and economic lithiations of functionalized arenes and heteroarenes using Cy2NLi in the presence of Mg, Zn or La halides in a continuous flow.

Project description:The economic amide base lithium dicyclohexylamide (Cy2NLi) allows fast and convenient (40 s, 0 °C) in situ trapping flow metalations of a broad range of functionalized arenes, heteroarenes and acrylate derivatives in the presence of various metal salts (ZnCl2·2LiCl, MgCl2, LaCl3·2LiCl). The resulting Zn-, Mg- or La-organometallic intermediates are trapped with various electrophiles in high yields. These flow metalations are easily scaled-up without further optimization.

| S-EPMC5802273 | 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