179249-16-2

Upstream product

• 459-57-4 4-fluorobenzaldehyde 
• 54012-23-6 1-(4-fluorophenyl)prop-2-yn-1-one 
• 108-05-4 vinyl acetate 
• 3798-61-6 1-(4-fluorophenyl)prop-2-yn-1-ol 
• 4301-14-8 acetylenemagnesium bromide 
• 179248-98-7 Chloro-acetic acid 1-(4-fluoro-phenyl)-prop-2-ynyl ester 
• 179249-05-9 Chloro-acetic acid (R)-1-(4-fluoro-phenyl)-prop-2-ynyl ester 
• 1066-54-2 trimethylsilylacetylene 

Downstream Products

• 179248-98-7 Chloro-acetic acid 1-(4-fluoro-phenyl)-prop-2-ynyl ester 
• 1190882-64-4 (3-(4-fluorophenyl)propa-1,2-dien-1-yl)diphenylphosphine oxide 

Relevant academic research and scientific papers

Multisubstituted pyrazole synthesis via [3?+?2] cycloaddition/rearrangement/N[sbnd]H insertion cascade reaction of α-diazoesters and ynones

The cascade reactions of alkyl α-diazoesters and ynones using Al(OTf)3 as the catalyst are described. A series of 4-substituted pyrazoles were obtained via [3 + 2] cycloaddition, 1,5-ester shift, 1,3-H shift, and N[sbnd]H insertion process. Deuterium labelling experiments, kinetic studies and control experiments were carried out for the rationalization of the mechanism.

Allenylidene Induced 1,2-Metalate Rearrangement of Indole-Boronates: Diastereoselective Access to Highly Substituted Indolines

A process to achieve 1,2-metalate rearrangements of indole boronate as a way to access substituted indolines in high diastereoselectivities is presented. The reaction involves the generation of a Cu–allenylidene, which is sufficiently electrophilic to induce the 1,2-metalate rearrangement. The scope of the reaction is evaluated as well as further transformations of the product.

Enantioselective [3 + 2] annulation of 4-isothiocyanato pyrazolones and alkynyl ketones under organocatalysis

An asymmetric [3 + 2] annulation reaction of 4-isothiocyanato pyrazolones with alkynyl ketones in the presence of an organic catalyst derived from a cinchona alkaloid under mild conditions is realized. This protocol provides unprecedented expeditious access to a wide range of optically active spiro[pyrroline-pyrazolones] with various electronic properties in high yields with good to excellent enantioselectivities.

Laccase-mediated Oxidations of Propargylic Alcohols. Application in the Deracemization of 1-arylprop-2-yn-1-ols in Combination with Alcohol Dehydrogenases

The catalytic system composed by the laccase from Trametes versicolor and the oxy-radical TEMPO has been successfully applied in the sustainable oxidation of fourteen propargylic alcohols. The corresponding propargylic ketones were obtained in most cases in quantitative conversions (87–>99 % yield), demonstrating the efficiency of the chemoenzymatic methodology in comparison with traditional chemical oxidants, which usually lead to problems associated with the formation of by-products. Also, the stereoselective reduction of propargylic ketones was studied using alcohol dehydrogenases such as the one from Ralstonia species overexpressed in E. coli or the commercially available evo-1.1.200, allowing the access to both alcohol enantiomers mostly with complete conversions and variable selectivities depending on the aromatic pattern substitution (97–>99 % ee). To demonstrate the compatibility of the laccase-mediated oxidation and the alcohol dehydrogenase-catalyzed bioreduction, a deracemization strategy starting from the racemic compounds was developed through a sequential one-pot two-step process, obtaining a selection of (S)- or (R)-1-arylprop-2-yn-1-ols with excellent yields (>98 %) and selectivities (>98 % ee) depending on the alcohol dehydrogenase employed.

Phosphorous acid promoted isomerization of propargyl alcohols to α,β-unsaturated carbonyl compounds

A metal-free and two-phase protocol for the Meyer-Schuster isomerization of propargyl alcohols to the corresponding α,β-unsaturated carbonyl compounds has been achieved in the presence of stoichiometric phosphorous acid aqueous solution, which produces the desired products in high yields with excellent stereoselectivity. Compared with the traditional methods, the procedure features broad scope of the substrates, mild conditions, and easy separation, providing an appealing alternative to the Meyer-Schuster reaction.

Palladium-catalyzed [3+2] annulation of allenyl carbinol acetates with C,N-cyclic azomethine imines

In this paper, a palladium-catalyzed [3+2] annulation of allenyl carbinol acetates with azomethine imines has successfully been developed under mild reaction conditions, affording biologically interesting tetrahydropyrazoloisoquinoline derivatives in high to excellent yields and with excellent stereoselectivity. The reaction follows a tandem [3+2] cycloaddition/allylation/elimination of AcOH pathway. Allenyl carbinol acetates also reacted well with in situ generated azomethine imine under cocatalysis of Ag(i)/Pd(0) catalysts in a similar reaction pathway.

Gem-Digold Acetylide Complexes for Catalytic Intermolecular [4 + 2] Cycloaddition: Having Two Gold Centers Is Better for Asymmetric Catalysis

Gold(I)-catalyzed highly enantioselective intermolecular [4 + 2] cycloaddition is shown with ynones and cyclohexadiene. Various bicyclo[2.2.2]octadiene derivatives are produced in high yields (up to 99%) with good enantioselectivity (up to 96% ee). Key to the success is generation of the gem-digold terminal alkyne as a catalytic on-cycle species. As proof of the gem-digold catalysis, a positive nonlinear effect is clarified between the ee's of the ligand and the cycloadduct.

Allenylic Carbonates in Enantioselective Iridium-Catalyzed Alkylations

An enantioconvergent C(sp3)-C(sp3) coupling between racemic allenylic electrophiles and alkylzinc reagents has been developed. An Ir/(phosphoramidite,olefin) catalyst provides access to highly enantioenriched allenylic substitution p

Copper- and borinic acid-catalyzed propargylic etherification of propargylic carbonates with benzyl alcohols

Propargylic substitution reactions have offered useful synthetic methods because further transformations based onthe alkyne moiety in the propargylic substituted products are readily achieved to construct more complex organic compounds. A large number of studies have been devoted to enantioselective propargylic substitution reactions with a variety of nucleophiles. However, successful examples of the use of alcohols as nucleophiles have been quite limited until now. To achieve utilization of aliphatic alcohols, herein we report the use of combined catalysis of a copper-pybox complex and a borinic acid. In this catalytic system, aliphatic alcohols such as benzyl alcohol derivatives were successfully applied to afford the corresponding propargylic etherified products in good yields with high enantioselectivities.

One-pot synthesis of polyfunctionalized quinolines: Via a copper-catalyzed tandem cyclization

An efficient one-pot approach for the synthesis of polyfunctionalized quinolines was developed via a sequence of copper-catalyzed coupling reaction/propargyl-allenyl isomerization/aza-electrocyclization. Easily available starting materials, mild conditions, and a wide substrate scope make this approach potentially useful.