Browse
Submit Data
Databases
API
Help

Dataset Information

20 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Key Mechanistic Features in Palladium-Catalyzed Methylcyclopropanation of Norbornenes With Vinyl Bromides: Insights From DFT Calculations.

ABSTRACT: DFT calculations were performed to elucidate mechanistic details of an unusual palladium-catalyzed methylcyclopropanation from [2 + 1] cycloadditions of (Z)-2-bromovinylbenzene and endo-N-(p-tolyl)-norbornenesuccinimide. The reaction proceeds via oxidative addition (OA), intermolecular alkene insertion, deprotonation/protonation, intramolecular alkene insertion, ?-H elimination and reductive elimination (RE). Protonation is the rate-limiting step and requires an overall barrier of 28.5 kcal/mol. The sources of two protons for protonation and exchange have also been clarified and the calculations agree with experimental observations.

SUBMITTER: Ying F

PROVIDER: S-EPMC6445852 | biostudies-literature | 2019

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Key Mechanistic Features in Palladium-Catalyzed Methylcyclopropanation of Norbornenes With Vinyl Bromides: Insights From DFT Calculations.

Ying Fang F Zhang Yutong Y Xiang Chuyue C Song Zhijun Z Xie Hujun H Bao Weiliang W

Frontiers in chemistry 20190327

DFT calculations were performed to elucidate mechanistic details of an unusual palladium-catalyzed methylcyclopropanation from [2 + 1] cycloadditions of (<i>Z</i>)-2-bromovinylbenzene and endo-N-(p-tolyl)-norbornenesuccinimide. The reaction proceeds via oxidative addition (OA), intermolecular alkene insertion, deprotonation/protonation, intramolecular alkene insertion, β-H elimination and reductive elimination (RE). Protonation is the rate-limiting step and requires an overall barrier of 28.5 kc ...[more]

PMID: 30972329

Similar Datasets

Palladium-Catalyzed Selective α-Alkenylation of Pyridylmethyl Ethers with Vinyl Bromides.

Project description:An efficient palladium-catalyzed α-alkenylation of pyridylmethyl ethers with vinyl bromides is presented. A Pd/NIXANTPHOS-based catalyst system enables a mild and chemoselective coupling between a variety of pyridylmethyl ethers and vinyl bromides in good to excellent yields. Under the mild conditions, β,γ-unsaturated products are obtained without isomerization or Heck byproducts observed.

| S-EPMC4887130 | biostudies-literature

Palladium-catalyzed conversion of aryl and vinyl triflates to bromides and chlorides.

Project description:The palladium-catalyzed conversion of aryl and vinyl triflates to aryl and vinyl halides (bromides and chlorides) has been developed using dialkylbiaryl phosphine ligands. A variety of aryl, heteroaryl, and vinyl halides can be prepared via this method in good to excellent yields.

| S-EPMC2975586 | biostudies-literature

An improved palladium-catalyzed conversion of aryl and vinyl triflates to bromides and chlorides.

Project description:A facile Pd-catalyzed conversion of aryl and vinyl triflates to aryl and vinyl halides (bromides and chlorides) is described. This method allows convenient access to a variety of aryl, heteroaryl, and vinyl halides in good to excellent yields and with greatly simplified conditions relative to our previous report.

| S-EPMC3170430 | biostudies-literature

Mechanistic Studies for Palladium Catalyzed Copolymerization of Ethylene with Vinyl Ethers.

Project description:The mechanism of ethylene with vinyl ether (VE, CH2=CHOEt) copolymerization catalyzed by phosphine-sulfonate palladium complex (A) was investigated by density functional theory (DFT) calculation. On achieving an agreement between theory and experiment, it is found that the favorable 1,2-selective insertion of VE into the complex A originates from stronger hydrogen interaction between the oxygen atom of VE and the ancillary ligand of catalyst A. Additionally, VE insertion is easier into the ethylene pre-inserted intermediate than that into the catalyst to form the resultant copolymers with the major units of OEt in chain and minor units of OEt at the chain end. The effect of β-OEt and β-H elimination was explored to elucidate chain termination and the molecular weight of copolymers. Furthermore, a family of cationic catalysts has been demonstrated to copolymerize ethylene with VE along with our modified cationic complex B with higher incorporation of VE and reactivity in comparison with complex A, which was modelled computationally by increasing the strong interactions between the catalyst and monomer moiety. Other than VE, the activity of cationic complex B for copolymerization of vinyl chloride and methacrylate is also computed successfully.

| S-EPMC7603233 | biostudies-literature

Synthesis of Spiroindenyl-2-Oxindoles through Palladium-Catalyzed Spirocyclization of 2-Bromoarylamides and Vinyl Bromides.

Project description:An expeditious approach to the construction of spiroindenyl-2-oxindoles was developed via a palladium-catalyzed spirocyclization reaction of 2-bromoarylamides with vinyl bromides. The reaction formed spiropalladacycles as the intermediates via carbopalladation and the C-H functionalization of 2-bromoarylamides. The spiropalladacycles reacted with vinyl bromides to form spiroindenyl-2-oxindoles. A Heck process rather than vinylic C-H functionalization was involved in the reaction.

| S-EPMC8704520 | biostudies-literature

A mild, palladium-catalyzed method for the dehydrohalogenation of alkyl bromides: synthetic and mechanistic studies.

Project description:We have exploited a typically undesired elementary step in cross-coupling reactions, ?-hydride elimination, to accomplish palladium-catalyzed dehydrohalogenations of alkyl bromides to form terminal olefins. We have applied this method, which proceeds in excellent yield at room temperature in the presence of a variety of functional groups, to a formal total synthesis of (R)-mevalonolactone. Our mechanistic studies have established that the rate-determining step can vary with the structure of the alkyl bromide and, most significantly, that L(2)PdHBr (L = phosphine), an intermediate that is often invoked in palladium-catalyzed processes such as the Heck reaction, is not an intermediate in the active catalytic cycle.

| S-EPMC3432975 | biostudies-literature

Palladium-catalyzed borylation of primary alkyl bromides.

Project description:A mild Pd-catalyzed process for the borylation of alkyl bromides has been developed using bis(pinacolato)diboron as a boron source. This process accommodates the use of a wide range of functional groups on the alkyl bromide substrate. Primary bromides react with complete selectivity in the presence of a secondary bromide. The generality of this approach is demonstrated by its extension to the use of alkyl iodides and alkyl tosylates, as well as borylation reactions employing bis(neopentyl glycolato)diboron as the boron source.

| S-EPMC3432578 | biostudies-literature

Mechanistic Studies of the Palladium-Catalyzed Desulfinative Cross-Coupling of Aryl Bromides and (Hetero)Aryl Sulfinate Salts.

Project description:Pyridine and related heterocyclic sulfinates have recently emerged as effective nucleophilic coupling partners in palladium-catalyzed cross-coupling reactions with (hetero)aryl halides. These sulfinate reagents are straightforward to prepare, stable to storage and coupling reaction conditions, and deliver efficient reactions, thus offering many advantages, compared to the corresponding boron-derived reagents. Despite the success of these reactions, there are only scant details of the reaction mechanism. In this study, we use structural and kinetic analysis to investigate the mechanism of these important coupling reactions in detail. We compare a pyridine-2-sulfinate with a carbocyclic sulfinate and establish different catalyst resting states, and turnover limiting steps, for the two classes of reagent. For the carbocyclic sulfinate, the aryl bromide oxidative addition complex is the resting state intermediate, and transmetalation is turnover-limiting. In contrast, for the pyridine sulfinate, a chelated Pd(II) sulfinate complex formed post-transmetalation is the resting-state intermediate, and loss of SO2 from this complex is turnover-limiting. We also investigated the role of the basic additive potassium carbonate, the use of which is crucial for efficient reactions, and deduced a dual function in which carbonate is responsible for the removal of free sulfur dioxide from the reaction medium, and the potassium cation plays a role in accelerating transmetalation. In addition, we show that sulfinate homocoupling is responsible for converting Pd(OAc)2 to a catalytically active Pd(0) complex. Together, these studies shed light on the challenges that must be overcome to deliver improved, lower temperature versions of these synthetically important processes.

| S-EPMC7146858 | biostudies-literature

Synthesis of N-Aryl-2-allyl Pyrrolidines via Palladium-catalyzed Carboamination Reactions of γ-(N-Arylamino)alkenes with Vinyl Bromides.

Project description:A palladium-catalyzed carboamination reaction of γ-N-arylamino alkenes with vinyl bromides that affords N-aryl-2-allyl pyrrolidines is described. These reactions proceed with high diastereoselectivity for the formation of trans-2,3- and cis-2,5-disubstituted pyrrolidines. Conditions for a tandem N-arylation/carboamination sequence that leads to the formation of an N-aryl-2-allyl pyrrolidine or indoline via the coupling of a primary γ-amino alkene, an aryl bromide, and a vinyl bromide are also reported. The mechanism of the carboamination reactions and the origin of unexpected products that formally derive from rearrangement of the vinyl bromide are discussed.

| S-EPMC2835409 | biostudies-literature

Palladium-catalyzed amination of unprotected five-membered heterocyclic bromides.

Project description:An efficient method for the palladium-catalyzed amination of unprotected bromoimidazoles and bromopyrazoles is presented. The transformation is facilitated by the use of our newly developed Pd precatalyst based on the bulky biarylphosphine ligand tBuBrettPhos (L4). The mild reaction conditions employed allow for the preparation of a broad scope of aminoimidazoles and aminopyrazoles in moderate to excellent yields.

| S-EPMC3983327 | 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