Browse
Submit Data
Databases
API
Help

Dataset Information

42 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Ring Opening of Triflates Derived from Benzophospholan-3-one Oxides by Aryl Grignard Reagents as a Route to 2-Ethynylphenyl(diaryl)phosphine Oxides.

ABSTRACT: A new simple method for the synthesis of 2-ethynylphenyl(diaryl)phosphine oxides via ring opening of benzophosphol-3-yl triflates has been developed. This process occurs via nucleophilic attack of a Grignard reagent at the phosphorus center, which results in ring opening and cleavage of a leaving group. The reaction proceeds under mild conditions and, within 15-60 min, leads to a library of previously unavailable 2-ethynylphenylphosphine oxides in yields up to 98%.

SUBMITTER: Ponikiewski L

PROVIDER: S-EPMC8576819 | biostudies-literature | 2021 Nov

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Ring Opening of Triflates Derived from Benzophospholan-3-one Oxides by Aryl Grignard Reagents as a Route to 2-Ethynylphenyl(diaryl)phosphine Oxides.

Ponikiewski Łukasz Ł Sowa Sylwia S

The Journal of organic chemistry 20211026 21

A new simple method for the synthesis of 2-ethynylphenyl(diaryl)phosphine oxides via ring opening of benzophosphol-3-yl triflates has been developed. This process occurs via nucleophilic attack of a Grignard reagent at the phosphorus center, which results in ring opening and cleavage of a leaving group. The reaction proceeds under mild conditions and, within 15-60 min, leads to a library of previously unavailable 2-ethynylphenylphosphine oxides in yields up to 98%. ...[more]

PMID: 34699223

Similar Datasets

Allenes in asymmetric catalysis: asymmetric ring opening of meso-epoxides catalyzed by allene-containing phosphine oxides.

Project description:Unsymmetrically substituted allenes (1,2-dienes) are inherently chiral and can be prepared in optically pure form. Nonetheless, to date the allene framework has not been incorporated into ligands for asymmetric catalysis. Since allenes project functionality differently than either tetrahedral carbon or chiral biaryls, they may create complementary chiral environments. This study demonstrates that optically active, C(2)-symmetric allene-containing bisphosphine oxides can catalyze the addition of SiCl(4) to meso-epoxides with high enantioselectivity. The epoxide opening likely involves generation of a Lewis acidic, cationic (bisphosphine oxide)SiCl(3) complex. The fact that high asymmetric induction is observed suggests that allenes may represent a new platform for the development of ligands and catalysts for asymmetric synthesis.

| S-EPMC2760382 | biostudies-literature

Continuous flow synthesis of diaryl ketones by coupling of aryl Grignard reagents with acyl chlorides under mild conditions in the ecofriendly solvent 2-methyltetrahydrofuran.

Project description:An efficient continuous flow sequential synthesis of diaryl ketones was achieved by coupling of aryl Grignard reagents with acyl chlorides in the bio-derived "green" solvent 2-methyltetrahydrofuran (2-MeTHF) under mild reaction conditions (ambient temperature, 1 hour), allowing a safe and on-demand generation of 2-(3-benzoylphenyl)propionitrile with a productivity of 3.16 g hour-1.

| S-EPMC9059842 | biostudies-literature

Intramolecular Ring-Opening Decomposition of Aryl Azetidines.

Project description:The ring strain present in azetidines can lead to undesired stability issues. Herein, we described a series of N-substituted azetidines which undergo an acid-mediated intramolecular ring-opening decomposition via nucleophilic attack of a pendant amide group. Studies were conducted to understand the decomposition mechanism enabling the design of stable analogues.

| S-EPMC8521649 | biostudies-literature

Practical Route for Catalytic Ring-Opening Metathesis Polymerization.

Project description:Norbornene derivatives are typical monomers for ring-opening metathesis polymerization (ROMP) for synthesizing highly functional polymers. However, the lack of catalytic methods, that is, the lack of readily available chain transfer agents (CTAs) for these monomers has been a significant cost limitation when large-scale syntheses are required. Here, we report commercially available styrene and its derivatives as efficient regioselective CTAs for the catalytic synthesis of metathesis polymers requiring up to 1000 times less ruthenium than in classical ROMP experiments. The molecular weight of the synthesized polymers was controlled by the monomer-to-CTA ratio. Low molecular weight ROMP polymers known for their antimicrobial properties were also synthesized on a gram scale in this report. Polymers were characterized by SEC, 1H NMR spectroscopy, and isotopically resolved MALDI-TOF MS. This approach describes a greener, more cost-effective, and eco-friendly methodology for the preparation of metathesis-based materials on the multigram scale.

| S-EPMC9795566 | biostudies-literature

Iron-Catalyzed C(sp2)-C(sp3) Cross-Coupling of Aryl Chlorobenzoates with Alkyl Grignard Reagents.

Project description:Aryl benzoates are compounds of high importance in organic synthesis. Herein, we report the iron-catalyzed C(sp2)-C(sp3) Kumada cross-coupling of aryl chlorobenzoates with alkyl Grignard reagents. The method is characterized by the use of environmentally benign and sustainable iron salts for cross-coupling in the catalytic system, employing benign urea ligands in the place of reprotoxic NMP (NMP = N-methyl-2-pyrrolidone). It is notable that high selectivity for the cross-coupling is achieved in the presence of hydrolytically-labile and prone to nucleophilic addition phenolic ester C(acyl)-O bonds. The reaction provides access to alkyl-functionalized aryl benzoates. The examination of various O-coordinating ligands demonstrates the high activity of urea ligands in promoting the cross-coupling versus nucleophilic addition to the ester C(acyl)-O bond. The method showcases the functional group tolerance of iron-catalyzed Kumada cross-couplings.

| S-EPMC6983197 | biostudies-literature

An oxidopyrylium cyclization/ring-opening route to polysubstituted ?-hydroxytropolones.

Project description:?-Hydroxytropolones are a class of molecules with therapeutic potential against several human diseases. However, structure-activity relationship studies on these molecules have been limited due to a scarcity of efficient synthetic methods to access them. It is demonstrated herein that ?-hydroxytropolones can be generated through a BCl(3)-mediated ring-opening/aromatization/demethylation process on 8-oxabicyclo[3.2.1]octenes. Used in conjunction with an improved method based on established oxidopyrylium dipolar cycloadditions, several polysubstituted ?-hydroxytropolones can be accessed in three steps from readily available ?-hydroxy-?-pyrones.

| S-EPMC3518617 | biostudies-literature

Coupling of Reformatsky Reagents with Aryl Chlorides Enabled by Ylide-Functionalized Phosphine Ligands.

Project description:The coupling of aryl chlorides with Reformatsky reagents is a desirable strategy for the construction of α-aryl esters but has so far been substantially limited in the substrate scope due to many challenges posed by various possible side reactions. This limitation has now been overcome by the tailoring of ylide-functionalized phosphines to fit the requirements of Negishi couplings. Record-setting activities were achieved in palladium-catalyzed arylations of organozinc reagents with aryl electrophiles using a cyclohexyl-YPhos ligand bearing an ortho-tolyl-substituent in the backbone. This highly electron-rich, bulky ligand enables the use of aryl chlorides in room temperature couplings of Reformatsky reagents. The reaction scope covers diversely functionalized arylacetic and arylpropionic acid derivatives. Aryl bromides and chlorides can be converted selectively over triflate electrophiles, which permits consecutive coupling strategies.

| S-EPMC7986804 | biostudies-literature

Iron-catalyzed cross-coupling of unactivated secondary alkyl thio ethers and sulfones with aryl Grignard reagents.

Project description:The first systematic investigation of unactivated aliphatic sulfur compounds as electrophiles in transition-metal-catalyzed cross-coupling are described. Initial studies focused on discerning the structural and electronic features of the organosulfur substrate that enable the challenging oxidative addition to the C(sp(3))-S bond. Through extensive optimization efforts, an Fe(acac)3-catalyzed cross-coupling of unactivated alkyl aryl thio ethers with aryl Grignard reagents was realized in which a nitrogen "directing group" on the S-aryl moiety of the thio ether served a critical role in facilitating the oxidative addition step. In addition, alkyl phenyl sulfones were found to be effective electrophiles in the Fe(acac)3-catalyzed cross-coupling with aryl Grignard reagents. For the latter class of electrophile, a thorough assessment of the various reaction parameters revealed a dramatic enhancement in reaction efficiency with an excess of TMEDA (8.0 equiv). The optimized reaction protocol was used to evaluate the scope of the method with respect to both the organomagnesium nucleophile and sulfone electrophile.

| S-EPMC3913001 | biostudies-literature

Cross-Coupling Reaction of Allylic Ethers with Aryl Grignard Reagents Catalyzed by a Nickel Pincer Complex.

Project description:A cross-coupling reaction of allylic aryl ethers with arylmagnesium reagents was investigated using β-aminoketonato- and β-diketiminato-based pincer-type nickel(II) complexes as catalysts. An β-aminoketonato nickel(II) complex bearing a diphenylphosphino group as a third donor effectively catalyzed the reaction to afford the target cross-coupled products, allylbenzene derivatives, in high yield. The regioselective reaction of a variety of substituted cinnamyl ethers proceeded to give the corresponding linear products. In contrast, α- and γ-alkyl substituted allylic ethers afforded a mixture of the linear and branched products. These results indicated that the coupling reaction proceeded via a π-allyl nickel intermediate.

| S-EPMC6631569 | biostudies-literature

Ammonium Salt-Catalyzed Ring-Opening of Aryl-Aziridines with ?-Keto Esters

Project description:We herein report an ammonium salt-catalyzed protocol for the regioselective ring opening of aryl-aziridines with ?-keto esters. The reaction gives access to a variety of highly functionalized target molecules with two consecutive stereo-genic centers and can be rendered enantioselective (up to e.r. = 91:9) by using bifunctional chiral ammonium salt catalysts.

| S-EPMC7116117 | 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