24243-06-9

Upstream product

• 6738-06-3 phenylethynylmagnesium bromide 
• 7577-74-4 6-acetoxy-6-methylcyclohexa-2,4-dienone 
• 108-24-7 acetic anhydride 
• 4440-01-1 lithium phenylacetylide 
• 141-78-6 ethyl acetate 
• 75-36-5 acetyl chloride 
• 60-29-7 diethyl ether 
• 536-74-3 phenylacetylene 
• 1817-57-8 4-phenyl-3-butyne-2-one 
• 15814-30-9 1,5-diphenyl-penta-1,4-diyn-3-one 
• 75-16-1 methylmagnesium bromide 

Downstream Products

• 1219035-60-5 (Z)-5-benzylidene-4-methyl-4-(phenylethynyl)-1,3-dioxolan-2-one 
• 1219035-61-6 (Z)-5-benzylidene-4-methyl-4-(phenylethynyl)-1,3-dioxolan-2-one 
• 1330527-47-3 3-methyl-4-oxo-1,5-diphenylpent-1-yn-3-yl diethylcarbamate 
• 1330527-50-8 3-methyl-4-oxo-1,5-diphenylpent-1-yn-3-yl tert-butylcarbamate 
• 1330527-51-9 3-methyl-4-oxo-1,5-diphenylpent-1-yn-3-yl isopropylcarbamate 
• 1330527-52-0 3-methyl-4-oxo-1,5-diphenylpent-1-yn-3-yl propylcarbamate 
• 1330527-53-1 3-methyl-4-oxo-1,5-diphenylpent-1-yn-3-yl allylcarbamate 

Relevant academic research and scientific papers

Ruthenabenzene: A Robust Precatalyst

Metallaaromatics constitute a unique class of aromatic compounds where one or more transition metal elements are incorporated into the aromatic system, the parent of which is metallabenzene. One of the main concerns about metallabenzenes generally deals with the structural characterization related to their relative aromaticity compared to the carbon archetype. Transition metal-containing metallabenzenes are also implicated in certain catalytic processes such as alkyne metathesis polymerization; however, these transition metal-based metallaaromatic compounds have not been developed as a catalyst. Herein, we describe an effective strategy to generate diverse arrays of ruthenabenzenes and demonstrated them as an aromatic equivalent of the Grubbs-type ruthenium alkylidene catalysts. These ruthenabenzenes can be prepared via an enyne metathesis and metallotropic [1,3]-shift cascade process to form alkyne-chelated ruthenium alkylidene intermediates followed by spontaneous cycloaromatization. The aromatic nature of these complexes was confirmed by spectroscopic and X-ray crystallographic data, and the mechanistic pathways for the cycloaromatization process were studied by DFT calculations. These ruthenabenzenes display robust catalytic activity for metathesis and other transformations, which illustrates that metallabenzenes are not only compounds of structural and theoretical interests but also are a novel platform for new catalyst development.

Gold-Catalyzed [4 + 1]-Annulation Reactions between 1,4-Diyn-3-ols and Isoxazoles to Construct a Pyrrole Core

This work reports gold-catalyzed [4 + 1]-annulation reactions between 1,4-diyn-3-ols and isoxazoles or benzisoxazoles to yield pyrrole derivatives. The reaction chemoselectivity is controlled by an initial attack of an isoxazole at a less hindered alkyne to form gold carbenes, further inducing a 1,2-migration of a second alkyne group. A broad substrate scope of 1,4-diyn-3-ols, isoxazoles and even benzisoxazoles highlighted the reaction utility.

Direct Substitution of Secondary and Tertiary Alcohols to Generate Sulfones under Catalyst- and Additive-Free Conditions

An environmentally benign protocol that affords propargylic sulfones containing highly congested carbon centers from easily accessible alcohols and sulfinic acids with water as the only byproduct is reported. The reaction proceeded via an in situ dehydrative cross-coupling process by taking advantage of the synergetic actions of multiple hydrogen bonds rather than relying on an external catalyst and/or additives to achieve high product distribution.

Gold-catalyzed N,O-functionalization of 1,4-diyn-3-ols with: N -hydroxyanilines to form highly functionalized pyrrole derivatives

This work describes new N,O-functionalization of 1,4-diyn-3-ols with N-hydroxyanilines to yield highly functionalized pyrrole derivatives. In a postulated mechanism, N-hydroxyaniline attacks the more electron-rich alkynes via regioselective N-attack to form unstable ketone-derived nitrones that react with their tethered alkynes via an intramolecular oxygen-transfer to form α-oxo gold carbenes. This new method is applicable to a short synthesis of a bioactive molecule, a PDE4 inhibitor.

Efficient large-scale synthesis of 4-phenyl-3-butyn-2-one, a key intermediate for a novel potent adenosine antagonist

Phenylacetylenic Grignard reagent reacts with acetic anhydride under mild conditions to give 4-phenyl-3-butyn-2-one in high yield. This method was applicable to a large-scale synthesis, and optimized reaction conditions have been investigated.