Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Synthesis of propargyl silanes from terminal alkynes via a migratory Sonogashira reaction.

ABSTRACT: Herein we report a mild synthesis of propargyl silanes from terminal alkynes. We exploit a bromonaphthyl-substituted silane as a silylmethyl electrophile surrogate, which participates in a Sonogashira reaction after an aryl-to-alkyl Pd-migration. Twenty-seven propargyl silanes were obtained in up to 88% yield. The obtained products were versatile building blocks that can be used in addition to electrophiles, triple bond hydrogenation or silyl group cleavage with acid or fluoride sources.

SUBMITTER: Purins M

PROVIDER: S-EPMC10286695 | biostudies-literature | 2023 Jun

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Synthesis of propargyl silanes from terminal alkynes via a migratory Sonogashira reaction.

Puriņš Mikus M Eichenberger Lucas L Waser Jérôme J

Chemical communications (Cambridge, England) 20230622 51

Herein we report a mild synthesis of propargyl silanes from terminal alkynes. We exploit a bromonaphthyl-substituted silane as a silylmethyl electrophile surrogate, which participates in a Sonogashira reaction after an aryl-to-alkyl Pd-migration. Twenty-seven propargyl silanes were obtained in up to 88% yield. The obtained products were versatile building blocks that can be used in addition to electrophiles, triple bond hydrogenation or silyl group cleavage with acid or fluoride sources. ...[more]

PMID: 37272881

Similar Datasets

Accessing alternative reaction pathways of the intermolecular condensation between homo-propargyl alcohols and terminal alkynes through divergent gold catalysis.

Project description:An intermolecular condensation of alkynols and terminal alkynes is reported. Using IPrAuNTf2, an efficient Au-catalyzed cyclization-alkynylation strategy furnishes (2-arylalkynyl) cyclic ethers in moderate to excellent yields (up to 94%). This strategy is extended to the synthesis of functionalized 2,3-dihydrooxepines via the sequential Au-catalyzed ring expansion of the cyclic ether substrates.

| S-EPMC5313346 | biostudies-literature

Synthesis of d-glyco-alkynone derivatives via carbonylative Sonogashira reaction.

Project description:A carbonylative Sonogashira coupling approach to the synthesis of glyco-alkynones is described. Eighteen examples were obtained in moderate do nearly quantitative yields under mild conditions employing Mo(CO)6 as a safe carbon monoxide source. Functionalization of the alkynyl moiety via cycloaddition with organic azides provided six examples of glyco-triazoles.

| S-EPMC9062118 | biostudies-literature

Radical reaction of sodium hypophosphite with terminal alkynes: synthesis of 1,1-bis-H-phosphinates.

Project description:[reaction: see text] The room-temperature radical addition of sodium hypophosphite to terminal alkynes produces the previously unknown 1-alkyl-1,1-bis-H-phosphinates in moderate yield. The reaction is initiated by R3B and air and proceeds under mild conditions in an open container. The bissodium salts precipitate spontaneously from the reaction mixtures, thus providing a simple purification procedure and the opportunity for multigram synthesis. The 1,1-bis-H-phosphinate products are novel precursors of the biologically important 1,1-bisphosphonates.

| S-EPMC2531071 | biostudies-literature

Synthesis of C4-alkynylisoxazoles via a Pd-catalyzed Sonogashira cross-coupling reaction.

Project description:A Pd-catalyzed Sonogashira cross-coupling reaction for the synthesis of C4-alkynylisoxazoles from 3,5-disubsitituted-4-iodoisoxazoles and terminal alkynes was described, which could afford the corresponding products with high yield (up to 98%). The results indicated that the steric effect from the group at the C3 position of the isoxazole had greater influence on the cross-coupling reaction than that from the group at the C5 position. In addition, the group at the C3 position of the isoxazole showed negligible electronic effects on the cross-coupling reaction. Furthermore, a gram-scale reaction of the Sonogashira coupling reaction was also investigated. Finally, a plausible mechanism for the Sonogashira coupling reaction was proposed.

| S-EPMC9061866 | biostudies-literature

Synthesis of Stereodefined 1,1-Diborylalkenes via Copper-Catalyzed Diboration of Terminal Alkynes.

Project description:A copper-catalyzed method for the E-selective 1,1-diboration of terminal alkynes is described. The tandem process involves sequential dehydrogenative borylation of the alkyne substrate with HBdan (1,8-diaminonaphthalatoborane), followed by hydroboration with HBpin (pinacolborane). This method proceeds efficiently under mild conditions, furnishing 1,1-diborylalkenes with excellent stereoselectivity and broad functional group tolerance. Taking advantage of the different reactivities of the two boryl moieties, the products can then be employed in stepwise cross-couplings with aryl halides for the stereocontrolled construction of trisubstituted alkenes.

| S-EPMC7391966 | biostudies-literature

Synthesis of unprotected glyco-alkynones via molybdenum-catalyzed carbonylative Sonogashira cross-coupling reaction.

Project description:Herein we report a novel Mo-catalyzed carbonylative Sonogashira cross-coupling between 2-iodoglycals and terminal alkynes. The reaction displays major improvements compared to a related Pd-catalyzed procedure previously published by our group, such as utilizing unprotected sugar derivatives as starting materials and tolerance to substrates bearing chelating groups. In this work we also demonstrate the utility of the glyco-alkynone products as platform for further functionalization by synthesizing glyco-flavones via Au-catalyzed 6-endo-dig cyclization.

| S-EPMC8979075 | biostudies-literature

Reaction Environment Design for Multigram Synthesis via Sonogashira Coupling over Heterogeneous Palladium Single-Atom Catalysts.

Project description:Single-atom heterogeneous catalysts (SACs) attract growing interest in their application in green chemistry and organic synthesis due to their potential for achieving atomic-level precision. These catalysts offer the possibility of achieving selectivity comparable to the traditionally applied organometallic complexes, while enhancing metal utilization and recovery. However, an understanding of SAC performance in organic reactions remains limited to model substrates, and their application as drop-in solutions may not yield optimal activity. Here, we investigate the previously unaddressed influence of the reaction environment, including solvent, base, cocatalyst, and ligand, on the performance of a palladium SAC in Sonogashira-Hagihara cross-couplings. By examining the effects of different solvents using the established criteria, we find that the behavior of the SAC deviates from trends observed with homogeneous catalysts, indicating a distinct interplay between heterogeneous systems and the reaction environment. Our results illustrate the satisfactory performance of SACs in cross-couplings of aryl iodides and acetylenes with electron-withdrawing and -donating groups, while the use of bromides and chlorides remains challenging. Extending the proof-of-concept stage to multigram scale, we demonstrate the synthesis of an intermediate of the anticancer drug Erlotinib. The catalyst exhibits high stability, allowing for multiple reuses, even under noninert conditions. Life-cycle assessment guides the upscaling of the catalyst preparation and quantifies the potential environmental and financial benefits of using the SAC, while also revealing the negligible impact of the PPh3 ligand and CuI cocatalyst. Our results underscore the significant potential of SACs to revolutionize sustainable organic chemistry and highlight the need for further understanding the distinct interplay between their performance and the reaction environment.

| S-EPMC10698743 | biostudies-literature

Synthesis of pyridines from ketoximes and terminal alkynes via C-H bond functionalization.

Project description:An expedient one-pot rhodium catalyzed C-H bond functionalization/electrocyclization/dehydration procedure has been developed for the synthesis of highly substituted pyridine derivatives from terminal alkynes and α,β-unsaturated ketoximes. The use of electron-deficient phosphite ligands is important to suppress dimerization of the terminal alkynes to enynes.

| S-EPMC3292635 | biostudies-literature

Cu-Catalyzed Transannulation Reaction of Pyridotriazoles with Terminal Alkynes under Aerobic Conditions: Efficient Synthesis of Indolizines.

Project description:The Cu(I)-catalyzed denitrogenative transannulation reaction of pyridotriazoles with terminal alkynes en route to indolizines was developed. Compared to the previously reported Rh-catalyzed transannulation reaction, this Cu-catalyzed method features aerobic conditions and much broader scope of pyridotriazoles and alkynes.

| S-EPMC4332698 | biostudies-literature

Enantioselective synthesis of cyclic carbamimidates via a three-component reaction of imines, terminal alkynes, and p-toluenesulfonylisocyanate using a monophosphine gold(I) catalyst().

Project description:A racemic Au(I)-catalyzed three-component reaction has been developed to prepare cyclic carbamimidates from imines, terminal alkynes, and sulfonylisocyanates. This reaction exploits the carbophilic π-acidity of gold catalysts to first activate an alkyne toward deprotonation and secondly, to activate the internal alkyne generated toward intramolecular O-cyclization. Unlike similar previously reported multicomponent gold-catalyzed reactions, the stereocenter generated during the alkynylation is preserved in the product. This trait was exploited by developing an enantioselective variant, using an unusual trans-1-diphenylphosphino-2-arylsulfamidocyclohexane ligand. Moderate to excellent levels of enantioselectivity were obtained using a variety of N-arylbenzylidene anilines (41-95% ee, 18 examples).

| S-EPMC3376162 | biostudies-literature