Iodonium metathesis reactions.
Ontology highlight
ABSTRACT:
SUBMITTER: Kasahara T
PROVIDER: S-EPMC5590373 | biostudies-literature | 2014 Sep
REPOSITORIES: biostudies-literature
Publications
Iodonium metathesis reactions.
Kasahara Takahito T Jang Young Jin YJ Racicot Léanne L Panagopoulos Dimitrios D Liang Steven H SH Ciufolini Marco A MA
Angewandte Chemie (International ed. in English) 20140714 36
A metathesis reaction occurs when a diaryliodonium triflate is heated with an aryl iodide, resulting in the formation of a new diaryliodonium triflate. ...[more]
Similar Datasets
Project description:Triphosphanes R'2PP(R)PR'2 (9a,c: R = Py; 9b R = BTz), 1,3-diphenyl-2-pyridyl-triphospholane 9d and pentaphospholanes (RP)5 (13: R = Py; 18: R = BTz) are obtained in high yield of up to 98% from the reaction of dipyrazolylphosphanes RPpyr2 (5: R = Py; 6: R = BTz; pyr = 1,3-dimethylpyrazolyl) and the respective secondary phosphane (R'2PH, R' = Cy (9a,b), t Bu (9c); PhPH(CH2)2PHPh (9d)). The formation of derivatives 9a-d proceeds via a condensation reaction while the formation of 13 and 18 can only be explained by a selective scrambling reaction. We realized that the reaction outcome is strongly solvent dependent as outlined by the controlled scrambling reaction pathway towards pentaphospholane 13. In our further investigations to apply these compounds as ligands we first confined ourselves to the coordination chemistry of triphosphane 9a with respect to coinage metal salts and discussed the observation of different syn- and anti-isomeric metal complexes based on NMR and X-ray analyses as well as quantum chemical calculations. Methylation reactions of 9a with MeOTf yield triphosphan-1-ium Cy2MePP(Py)PCy2 + (10 +) and triphosphane-1,3-diium Cy2MePP(Py)PMeCy2 2+ (11 2+) cations as triflate salts. Salt 11[OTf]2 reacts with pentaphospholane 13 in an unprecedented chain growth reaction to give the tetraphosphane-1,4-diium triflate salt Cy2MePP(Py)P(Py)PMeCy2 2+ (19[OTf]2) via a P-P/P-P bond metathesis reaction. The latter salt is unstable in solution and rearranges via a rare [1,2]-migration of the Cy2MeP-group followed by the elimination of the triphosph-2-en-1-ium cation [Cy2MePPPMeCy2]+ (20 +) to yield a novel 1,4,2-diazaphospholium salt (21[OTf]).
| S-EPMC7066665 | biostudies-literature
Project description:Transannular carbonyl-olefin metathesis reactions complement existing procedures for related ring-closing, ring-opening, and intermolecular carbonyl-olefin metathesis. We herein report the development and mechanistic investigation of FeCl3-catalyzed transannular carbonyl-olefin metathesis reactions that proceed via a distinct reaction path compared to previously reported ring-closing and ring-opening protocols. Specifically, carbonyl-ene and carbonyl-olefin metathesis reaction pathways are competing under FeCl3-catalysis to ultimately favor metathesis as the thermodynamic product. Importantly, we show that distinct Lewis acid catalysts are able to distinguish between these pathways to enable the selective formation of either transannular carbonyl-ene or carbonyl-olefin metathesis products. These insights are expected to enable further advances in catalyst design to efficiently differentiate between these two competing reaction paths of carbonyl and olefin functionalities to further expand the synthetic generality of carbonyl-olefin metathesis.
| S-EPMC6979496 | biostudies-literature
Project description:The carbonyl-olefin metathesis (COM) reaction is a highly valuable chemical transformation in a broad range of applications. However, its scope is much less explored compared to analogous olefin-olefin metathesis reactions. Herein we demonstrate the use of tropylium ion as a new effective organic Lewis acid catalyst for both intramolecular and intermolecular COM and new ring-opening metathesis reactions. This represents a significant improvement in substrate scope from recently reported developments in this field.
| S-EPMC6000984 | biostudies-literature
Project description:Dimethyl (?-substituted) vinylphosphonates do not readily undergo cross metathesis reactions with Grubbs catalyst and terminal alkenes. However, the corresponding mono- or diallyl vinylphosphonate esters undergo facile cross metathesis reactions. The improved reactivity is attributed to a relay step in the cross metathesis reaction mechanism.
| S-EPMC4168886 | biostudies-other
Project description:Difluoromethanesulfonyl hypervalent iodonium ylides 2 were developed as electrophilic difluoromethylthiolation reagents for a wide range of nucleophiles. Enamines, indoles, ?-keto esters, silyl enol ethers and pyrroles were effectively reacted with 2 affording desired difluoromethylthio (SCF2H)-substituted compounds in good to high yields under copper catalysis. The reaction of allyl alcohols with 2 under the same conditions provided difluoromethylsulfinyl (S(O)CF2H) products in good yields. The difluoromethylthiolation of enamines is particularly effective with wide generality, thus the enamine method was nicely extended to the synthesis of a series of difluoromethythiolated cyclic and acyclic ?-keto esters, 1,3-diketones, pyrazole and pyrimidine derivatives by a consecutive, two-step one-pot reaction using 2.
| S-EPMC4892452 | biostudies-literature
Project description:The BP unsaturated unit is a very attractive functional group as it provides novel reactivity and unique physical properties. Nonetheless, applications remain limited so far due to the bulky nature of B/P-protecting groups, required to prevent oligomerization. Herein, we report the synthesis and isolation of a N-heterocyclic carbene (NHC)-stabilized phosphaborene, bearing a trimethylsilyl (TMS) functionality at the P-terminal, as a room-temperature-stable crystalline solid accessible via facile NHC-induced trimethylsilyl chloride (TMSCl) elimination from its phosphinoborane precursor. This phosphaborene compound, bearing a genuine B=P bond, exhibits a remarkable ability for undergoing P-centre metathesis reactions, which allows the isolation of a series of unprecedented phosphaborenes. X-ray crystallographic analysis, UV/Vis spectroscopy, and DFT calculations provide insights into the B=P bonding situation.
| S-EPMC9401048 | biostudies-literature
Project description:The development of catalyst-controlled stereoselective olefin metathesis processes has been a pivotal recent advance in chemistry. The incorporation of appropriate ligands within complexes based on molybdenum, tungsten and ruthenium has led to reactivity and selectivity levels that were previously inaccessible. Here we show that molybdenum monoaryloxide chloride complexes furnish higher-energy (Z) isomers of trifluoromethyl-substituted alkenes through cross-metathesis reactions with the commercially available, inexpensive and typically inert Z-1,1,1,4,4,4-hexafluoro-2-butene. Furthermore, otherwise inefficient and non-stereoselective transformations with Z-1,2-dichloroethene and 1,2-dibromoethene can be effected with substantially improved efficiency and Z selectivity. The use of such molybdenum monoaryloxide chloride complexes enables the synthesis of representative biologically active molecules and trifluoromethyl analogues of medicinally relevant compounds. The origins of the activity and selectivity levels observed, which contradict previously proposed principles, are elucidated with the aid of density functional theory calculations.
| S-EPMC5748242 | biostudies-literature
Project description:A tremendous number of solvents, either as liquids or vapors, contaminate the environment on a daily basis worldwide. Olefin metathesis, which has been widely used as high-yielding protocols for ring-opening metathesis polymerization (ROMP), ring-closing metathesis (RCM), and isomerization reactions, is typically performed in toxic and volatile solvents such as dichloromethane. In this study, the results of our systematic experiments with the Grubbs G1, G2, and Hoveyda-Grubbs HG2 catalysts proved that benzotrifluoride (BTF) can replace dichloromethane (DCM) in these reactions, providing high yields and similar or even higher reaction rates in certain cases. The ROMP of norbornene resulted not only in high yields but also in polynorbornenes with a high molecular weight at low catalyst loadings. Ring-closing metathesis (RCM) experiments proved that, with the exception of the G1 catalyst, RCM occurs with similar high efficiencies in BTF as in DCM. It was found that isomerization of (Z)-but-2-ene-1,4-diyl diacetate with the G2 and HG2 catalysts proceeds at significantly higher initial rates in BTF than in DCM, leading to rapid isomerization with high yields in a short time. Overall, BTF is a suitable solvent for olefin metathesis, such as polymer syntheses by ROMP and the ring-closing and isomerization reactions.
| S-EPMC9820898 | biostudies-literature
Project description:Copper iodide has been shown to be an effective cocatalyst for the olefin cross-metathesis reaction. In particular, it has both a catalyst stabilizing effect due to iodide ion, as well as copper(I)-based phosphine-scavenging properties that apply to use of the Grubbs-2 catalyst. A variety of Michael acceptors and olefinic partners can be cross-coupled under mild conditions in refluxing diethyl ether that avoid chlorinated solvents. This effect has also been applied to chemistry in water at room temperature using the new surfactant TPGS-750-M.
| S-EPMC3352770 | biostudies-literature
Project description:The bis(cyclopentadienyl)(tert-butylimido)zir-conium complex 1 undergoes ambient-temperature metathesis reactions with nitro- and nitrosoarenes, providing a rare nonphotochemical synthesis of cis-azoxy and cis-azo compounds, respectively. 2-Nitro-2-methylpropane also undergoes metathesis to give trans-(tert-butylazoxy)-2-methylpropane. This reaction was studied kinetically, and the rate was found to be first order in both 1 and substrate and inversely proportional to the concentration of tetrahydrofuran, with activation parameters DeltaH(double dagger) = 15 +/- 2 kcal mol(-1) and DeltaS(double dagger) = -26 +/- 3 cal mol(-1) K(-1).
| S-EPMC1383656 | biostudies-literature