Browse
Submit Data
Databases
API
Help

Dataset Information

21 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Zirconocene catalyzed diastereoselective carbometalation of cyclobutenes.

ABSTRACT: The regio- and diastereoselective zirconocene-catalyzed carbomagnesiation of cyclobutenes is herein reported to afford configurationally stable cyclobutylmagnesium species that could subsequently react with a large variety of electrophiles to give polysubstituted cyclobutane species as a single diastereoisomer.

SUBMITTER: Roy SR

PROVIDER: S-EPMC5365058 | biostudies-literature | 2017 Jan

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Zirconocene catalyzed diastereoselective carbometalation of cyclobutenes.

Roy Sudipta Raha SR Eijsberg Hendrik H Bruffaerts Jeffrey J Marek Ilan I

Chemical science 20160830 1

The regio- and diastereoselective zirconocene-catalyzed carbomagnesiation of cyclobutenes is herein reported to afford configurationally stable cyclobutylmagnesium species that could subsequently react with a large variety of electrophiles to give polysubstituted cyclobutane species as a single diastereoisomer. ...[more]

PMID: 28451177

Similar Datasets

Palladium-Catalyzed Oxidative Carbocyclization-Borylation of Enallenes to Cyclobutenes.

Project description:A highly efficient palladium-catalyzed oxidative borylation of enallenes was developed for the selective formation of cyclobutene derivatives and fully-substituted alkenylboron compounds. Cyclobutenes are formed as the exclusive products in MeOH in the presence of H2 O and Et3 N, whereas the use of AcOH leads to alkenylboron compounds. Both reactions showed a broad substrate scope and good tolerance for various functional groups, including carboxylic acid ester, free hydroxy, imide, and alkyl groups. Furthermore, transformations of the borylated products were conducted to show their potential applications.

| S-EPMC5021125 | biostudies-literature

Bimetallic Zr,Zr-Hydride Complexes in Zirconocene Catalyzed Alkene Dimerization.

Project description:Being valuable precursors in the production of adhesives, lubricants, and other high-performance synthetic compounds, alkene dimers and oligomers can be obtained using homogeneous zirconocene catalytic systems. Further advances in such systems require precise control of their activity and chemoselectivity, increasing both the purity and yield of the products. This relies on the process mechanism usually built around the consideration of the hydride complexes as active intermediates in the alkene di- and oligomerization; however, the majority of studies lack the direct evidence of their involvement. Parallel studies on a well-known Cp2ZrCl2-AlR3 or HAlBui2 and a novel [Cp2ZrH2]2-ClAlR2 (R = Me, Et, Bui) systems activated by methylaluminoxane (MMAO-12) have shown a deep similarity both in the catalytic performance and intermediate composition. As a result of the NMR studies, among all the intermediates considered, we proved that new Zr,Zr- hydride complexes having the type x[Cp2ZrH2∙Cp2ZrHCl∙ClAlR2]∙yMAO appear to be specifically responsible for the alkene dimerization with high yield.

| S-EPMC7248859 | biostudies-literature

Base-catalyzed diastereoselective trimerization of trifluoroacetone.

Project description:Amphiphilic fluorocarbons have unique properties that facilitate their self assembly and adhesion to both inorganic and biological substrates. Incorporation of these moieties into valuable constructs typically require complex synthetic routes that have limited their use. Here, the base-catalyzed diastereoselective synthesis of 6-methyl-2,4,6-tris(trifluoromethyl)tetrahydro-2H-pyran-2,4-diol is reported. Trimerization of trifluoroacetone in the presence of 5 mol% KHMDS delivers one of four diastereomers selectively in 81% yield with no column chromatography. Temperature screening revealed the reversibility of this trimerization and the funneling of material into the most thermodynamically stable oxane. Subsequent functionalization with boronic acids is reported.

| S-EPMC5584686 | biostudies-literature

Diastereoselective, Zinc-Catalyzed Alkynylation of ?-Bromo Oxocarbenium Ions.

Project description:We have developed a bromination/alkynylation sequence that enables efficient transformation of simple cyclic enol ethers to difunctionalized products. The success of this strategy relies on a highly diastereselective, zinc-catalyzed addition of terminal alkynes to ?-bromo oxocarbenium ions, formed in situ via ionization of acetal precursors. Using this method, trans-?-alkynyl-?-halo pyran and furan derivatives can be prepared with high diastereoselectivity and excellent functional group tolerance.

| S-EPMC4820761 | biostudies-literature

Diastereoselective Ni-catalyzed 1,4-hydroboration of chiral dienols.

Project description:The Ni-catalyzed hydroboration of dienols occurs in a 1,4 fashion and delivers a syn-propionate motif in high diastereoselectivity and with a stereodefined trisubstituted crotylboronic ester. The boronic ester can be further manipulated to provide carbon-carbon or carbon-oxygen bonds.

| S-EPMC4444069 | biostudies-literature

Diastereoselective Pt catalyzed cycloisomerization of polyenes to polycycles.

Project description:Application of a tridentate NHC containing pincer ligand to Pt catalyzed cascade cyclization reactions has allowed for the catalytic, diastereoselective cycloisomerization of biogenic alkene terminated substrates to the their polycyclic counterparts.

| S-EPMC3985707 | biostudies-literature

Zirconocene-Catalyzed Dimerization of ?-Olefins: DFT Modeling of the Zr-Al Binuclear Reaction Mechanism.

Project description:Zirconocene-mediated selective dimerization of ?-olefins usually occurs when precatalyst (?5-C5H5)2ZrCl2 is activated by minimal excess of methylalumoxane (MAO). In this paper, we present the results of density functional theory (DFT) simulation of the initiation, propagation, and termination stages of dimerization and oligomerization of propylene within the framework of Zr-Al binuclear mechanism at M-06x/DGDZVP level of theory. The results of the analysis of the reaction profiles allow to explain experimental facts such as oligomerization of ?-olefins at high MAO/(?5-C5H5)2ZrCl2 ratios and increase of the selectivity of dimerization in the presence of R2AlCl. The results of DFT simulations confirm the crucial role of the presence of chloride in the selectivity of dimerization. The molecular hydrogen was found in silico and proven experimentally as an effective agent that increases the rate and selectivity of dimerization.

| S-EPMC6803839 | biostudies-literature

Cobalt-Catalyzed Diastereoselective and Enantioselective Hydrosilylation of Achiral Cyclopropenes.

Project description:A mild diastereoselective and enantioselective cobalt-catalyzed hydrosilylation reaction of achiral cyclopropenes has been developed. In this protocol, various substituted cyclopropenes and arylsilanes were transformed, in the presence of readily available chiral cobalt complex, into silylcyclopropanes with high selectivities.

| S-EPMC7467819 | biostudies-literature

Lewis acid-catalyzed diastereoselective hydroarylation of benzylidene malonic esters.

Project description:Herein we report that simple Lewis acids catalyze the hydroarylation of benzylidene malonates with phenols. Ultimately, 3,4-disubstituted dihydrocoumarins are obtained via a hydroarylation-lactonization sequence. Moreover, the dihydrocoumarins are formed with a high degree of diastereoselectivity favoring the trans stereoisomer.

| S-EPMC2882201 | biostudies-literature

Iron-Catalyzed Diastereoselective Intramolecular Olefin Aminobromination with Bromide Ion.

Project description:A new iron-catalyzed diastereoselective aminobromination method is reported for both internal and terminal olefins (yield up to 90% and dr up to >20:1). In this transformation, a functionalized hydroxylamine and bromide ion were used as the nitrogen and bromine source, respectively. This method is compatible with a broad range of olefins and provides a convenient approach to synthetically valuable vicinal bromo primary amines. Our studies suggest that both the diastereoselectivity and enantioselectivity for the olefin aminobromination can be controlled by iron catalysts.

| S-EPMC4720155 | 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