222713-56-6

Usage

Chemical compound

Benzenemethanol, 2-bromo-a-ethynyl-

Properties

Halogenated derivative of benzenemethanol containing a bromine atom and an ethynyl group

Uses

Synthesis of pharmaceuticals and agrochemicals, production of fine chemicals and dyes

Reactivity

Ability to undergo substitution, addition, and condensation reactions

Importance

Valuable and important compound in organic chemistry.

Upstream product

• 65032-27-1 ethynylmagnesium chloride 
• 6630-33-7 ortho-bromobenzaldehyde 
• 74-86-2 acetylene 
• 1066-54-2 trimethylsilylacetylene 
• 4301-14-8 acetylenemagnesium bromide 

Downstream Products

• 1262149-01-8 1-(2-bromophenyl)-2-oxopropyl acetate 
• 1427777-87-4 C₁₄H₁₂BrF₃O₅S 
• 66223-53-8 trans-2-bromocinnamaldehyde 

Relevant academic research and scientific papers

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.

Coupling-Isomerization-Cycloisomerization Reaction (CICIR) – An Unexpected and Efficient Domino Approach to Luminescent 2-(Hydroxymethylene)indenones

A Pd/Cu-catalyzed base mediated domino process of ortho-halo (hetero)aryl carboxaldehydes and propargyl alcohols unexpectedly furnish 2-(hydroxymethylene)indenones in good to excellent yield as a result of a coupling-isomerization-cycloisomerization reaction (CICIR). In addition, the title compounds constitute an interesting class of luminophores with tunable emission solvatochromicity.

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.

Trialkylborane-Mediated Propargylation of Aldehydes Using γ-Stannylated Propargyl Acetates

A transition-metal-free three-component process that combines aldehydes, 3-(tributylstannyl)propargyl acetates formed in situ from readily available propargyl acetates, and trialkylboranes provides access to a range of 1,2,4-trisubstituted homopropargylic alcohols. The addition of diisopropylamine plays a crucial role in the selective formation of homopropargylic alcohols. Importantly, this methodology can be extended to a single-flask reaction sequence starting from propargyl acetates.

Trialkylborane-Mediated Multicomponent Reaction for the Diastereoselective Synthesis of Anti-δ,δ-Disubstituted Homoallylic Alcohols

The trialkylborane/O2-mediated reaction of propargyl acetates having a tributylstannyl group at an alkyne terminus with aldehydes in a THF-H2O solvent system gave anti-δ,δ-disubstituted homoallylic alcohols with good to high diastereoselectivity. Intriguingly, two alkyl groups derived from trialkylborane were embedded into the reaction product. The trialkylborane plays a key role not only as a radical initiator but also as a source of alkyl radicals.

Nitromethane as a Carbanion Source for Domino Benzoannulation with Ynones: One-Pot Synthesis of Polyfunctional Naphthalenes and a Total Synthesis of Macarpine

A one-pot, transition-metal-free, domino Michael/SNAr protocol of general applicability has been devised for the regioselective synthesis of polyfunctional naphthalenes by employing nitromethane and ortho-haloaryl ynones. Utilization of nitromethane as a one carbon carbanion source that is incorporated into a variety of ynones, ends up as an aromatic nitro substituent. The application of this domino process towards a total synthesis of the polycyclic alkaloid macarpine demonstrate for the efficacy of this methodology. The conceptually simple approach to affect regioselective, multifunctional benzoannulation of ynones displays wide substrate scope and functional-group tolerance and has been implemented with substituted nitromethanes, as well as with alicyclic o-haloynones.

A novel synthesis of N-hydroxy-3-aroylindoles and 3-aroylindoles

A straightforward indole synthesis via annulation of C-nitrosoaromatics with conjugated terminal alkynones was realised achieving a simple, highly regioselective, atom- and step economical access to 3-aroylindoles in moderate to good yields. Further functionalizations of indole scaffolds were investigated and an easy way to JWH-018, a synthetic cannabinoid, was achieved.

A novel selenoflavone compound as anti-obesity agent

The present invention relates to a process for producing a novel selenoflavone compound and a pharmaceutical composition for preventing or treating obesity comprising the selenoflavone compound. In the present invention, selenoflavone, especially PMSF, which has never been synthesized due to synthetic difficulties can be synthesized through palladium-catalyzed direct C-H arylation. Since the synthesized selenoflavone has an improving effect related to activation of brown adipose tissue (BAT), the selenoflavone can be used in the composition for prevention and treatment of obesity.COPYRIGHT KIPO 2018

Efficient synthesis of polymethoxyselenoflavones via regioselective direct C-H arylation of selenochromones

Substantial research has suggested that the configuration and the total number of functional groups on flavones influence their bioactivity. To investigate the changes in the biological activities of selenoflavones in relationship to structural changes, the development of a generally applicable synthetic method was a key. Until now, an efficient pathway for palladium-catalyzed direct arylation with the selenocyclic enone systems is not known in the literature. We herein introduce a simple direct C-H arylation of two difficult coupling partners, selenochromones and electron-rich aryl bromide, affording diverse polymethoxyselenoflavones with great efficiency and high selectivity.