396717-17-2

Upstream product

• 931-48-6 2-cyclohexylacetylene 
• 6630-33-7 ortho-bromobenzaldehyde 
• 1039078-20-0 2-(cyclohexylethynyl)benzaldehyde O-phenyl oxime 
• 626-62-0 Cyclohexyl iodide 
• 38846-64-9 2-ethynylbenzaldehyde 
• 77123-58-1 2-[2-(trimethylsilyl)ethynyl]benzaldehyde 
• 89-98-5 2-chloro-benzaldehyde 

Downstream Products

• 1039078-20-0 2-(cyclohexylethynyl)benzaldehyde O-phenyl oxime 
• 1196480-64-4 (4E)-2-cyclohexyl-3-cyclohexylimino-4-cyclohexylmethylene-3,4-dihydro-2H-isoquinolin-1-one 
• 1256286-18-6 methyl 2-(cyclohexylethynyl)benzoate 
• 1364406-37-0 (S)-8-bromo-12-cyclohexyl-4b,5-dihydroisoquinolino[2,1-a]quinazolin-6-one 
• 1443761-92-9 12-cyclohexyl-4b,6-dihydrobenzo[4,5][1,3]oxazino[2,3-a]isoquinoline 

Relevant academic research and scientific papers

A Mild and Regioselective Synthesis of α-Fluoroketones via Gold and Selectfluor Partnership

An efficient, mild and rapid synthesis of α-fluoroketones has been developed, via a fruitful association between gold and Selectfluor starting from aldehyde-yne and alkynylaryl ketone derivatives. Several functionalized and synthetically highly valuable α-fluoroketones (21 compounds, up to 92%) were isolated in good to excellent yields via a remarkable regioselective oxyfluorination reaction in EtOH/H2O at room temperature. We have shed some light on parts of the mechanism by reacting diphenylacetylene and aldehyde-yne with or without Selectfluor. The reaction most presumably occurs via a sequential gold-catalyzed regioselective hydration followed by the α-fluorination reaction, but the presence of aldehyde moiety is crucial for the reactivity of alkyne function. The fluoroketones were efficiently transformed to 4-fluoroisoquinolines (9 compounds, 82–95%) of high pharmaceutical interest. (Figure presented.).

Catalytic Asymmetric 1,3-Dipolar Cycloaddition/Hydroamination Sequence: Expeditious Access to Enantioenriched Pyrroloisoquinoline Derivatives

A three-step reaction sequence has been developed to prepare a variety of enantioenriched pyrroloisoquinoline derivatives. The process involves a catalytic asymmetric azomethine ylide 1,3-dipolar cycloaddition followed by an intramolecular AuI-catalyzed alkyne hydroamination and enamine reduction.

Gold(I)-catalyzed cycloisomerizations and alkoxycyclizations of ortho-(alkynyl)styrenes

Indenes and related polycyclic structures have been efficiently synthesized by gold(I)-catalyzed cycloisomerizations of appropriate ortho-(alkynyl)styrenes. Disubstitution at the terminal position of the olefin was demonstrated to be essential to obtain products originating from a formal 5-endo-dig cyclization. Interestingly, a complete switch in the selectivity of the cyclization of o-(alkynyl)-a-methylstyrenes from 6-endo to 5-endo was observed by adding an alcohol to the reaction media. This allowed the synthesis of interesting indenes bearing an all-carbon quaternary center at C1. Moreover, dihydrobenzo[a]fluorenes can be obtained from substrates bearing a secondary alkyl group at the β-position of the styrene moiety by a tandem cycloisomerization/1,2-hydride migration process. In addition, diverse polycyclic compounds were obtained by an intramolecular gold-catalyzed alkoxycyclization of o-(alkynyl)styrenes bearing a nucleophile in their structure. Finally, the use of a chiral gold complex allowed access to elusive chiral 1H-indenes in good enantioselectivities.

On water: Silver-catalyzed domino approach for the synthesis of benzoxazine/oxazine-fused isoquinolines and naphthyridines from o-alkynyl aldehydes

An operationally simple domino approach for the silver-catalyzed synthesis of oxazine/benzoxazine-fused isoquinolines 5a-q and naphthyridines 6a-v by the reaction of o-alkynyl aldehydes 3a-aa with amines having embedded nucleophiles 4a-d under mild reacti

Grignard reagent/CuI/LiCl-mediated stereoselective cascade addition/cyclization of diynes: A novel pathway for the construction of 1-methyleneindene derivatives

Diynes containing a cyclopropane group smoothly undergo a novel intramolecular and stereoselective cascade addition/cyclization reaction to produce the corresponding 1-methyleneindene derivatives in moderate to good yields. This interesting transformation is mediated by Grignard reagent/CuI with LiCl as an additive under mild conditions. The obtained product can easily be further functionalized through cyclopropyl ring opening. A plausible reaction mechanism has also been presented on the basis of deuterium labeling and control experiments. Diyne cyclization: Diynes containing a cyclopropane group undergo a novel intramolecular and stereoselective cascade addition/cyclization reaction to produce the corresponding 1-methyleneindene derivatives (see scheme). The transformation proceeds under mild conditions and is promoted by a combination of Grignard reagent Copyright

A CuBr-mediated aerobic reaction of 2-alkynylbenzaldehydes and primary amines: Synthesis of 4-bromoisoquinolones

A method for synthesis of 4-bromoisoquinolones has been developed starting from 2-alkynylbenzaldehydes and primary amines mediated by CuBr under an O 2 atmosphere, where CuBr plays multiple roles to facilitate the present reactions.

Simple gold-catalyzed synthesis of benzofulvenes-gem-Diaurated species as "instant dual-activation" precatalysts

Alkyl-substituted diynes deliver benzofulvenes in a unique gold-catalyzed reaction. The catalytic cycle involves the formation of gold acetylides by alkynyl C-H activation, the formation of vinylidene gold(I) intermediates by dual activation, and alkyl C-H activation by the vinylidene gold(I) species. gem-Diaurated species obtained from the catalysis reactions prove to be highly active catalysts for these conversions. Copyright

AgI-catalyzed cascade strategy: Regioselective access to diversely substituted fused benzimidazo[2,1-a]isoquinolines, naphthyridines, thienopyridines, and quinoxalines in water

An environmentally benign and operationally simple one-pot approach to the regioselective tandem synthesis of diversely substituted fused benzimidazo[2,1-a]isoquinolines, naphthyridines, thienopyridines, and quinoxalines from o-alkynylaldehydes and arylamines with tethered nucleophiles using AgI as catalyst in water is described. The reaction showed selective N-C bond formation on the more electrophilic alkynyl carbon, resulting in the regioselective 6-endo-dig cyclized products in good to excellent yields. The proposed mechanistic pathway for the synthesis of fused heterocycles proceeding through formation of ring A prior to ring B, which formed through a second intramolecular attack of the nitrogen onto the alkynyl carbon, was supported by mechanistic experiments and X-ray crystallographic studies of isolated intermediate U and cyclized product 5a. Comparative experiments showed the viability of intramolecular nucleophilic attack over intermolecular attack of an external nucleophile. This catalytic, green protocol has been efficiently applied for the bis-tandem cyclization in water. An eco-friendly, one-pot cascade approach to benzimidazoles and quinoxalines in water using AgNO 3 as catalyst from o-alkynyl aldehydes and amines with tethered nucleophiles, has been developed. Selective 6-endo-dig regioselectivity and structural diversity are accomplished in good yields with a range of substrates. X-ray crystallographic studies and mechanistic experiments are also presented. Copyright

Gold-catalyzed oxidative cyclizations of 2-oxiranyl-1-alkynylbenzenes for diastereoselective synthesis of highly substituted 2-hydroxyindanones

We report the gold-catalyzed oxidative cyclizations of 2-oxiranyl-1- alkynylbenzenes into highly substituted 2-hydroxyindanone frameworks bearing a tertiary alcohol. Such gold-catalyzed reactions comprise an initial internal redox reaction, sulfoxide oxidation of α-carbonyl gold-carbenoids, followed by gold-catalyzed formal ene reactions on the resulting diketone intermediates. Copyright

Iodine-mediated solvent-controlled selective electrophilic cyclization and oxidative esterification of o-alkynyl aldehydes: An easy access to pyranoquinolines, pyranoquinolinones, and isocumarins

Chemoselective behavior of iodine in different solvents in the electrophilic iodocyclization of o-alkynyl aldehydes is described. o-Alkynyl aldehydes 3a-t on reaction with I2 in CH2Cl2 with appropriate nucleophiles provides pyrano[4,3-b]quinolines 4a-f, via formation of cyclic iodonium intermediate Q; however, using alcohols as a solvent as well as nucleophile, o-alkynyl esters 5a-y were obtained selectively in good to excellent yields via formation of hypoiodide intermediate R. Subsequently, o-alkynyl esters were converted in to pyranoquinolinones 6a-i and isocoumarin 6j by electrophilic iodocyclization. This developed oxidative esterification provides a novel access for the chemoselective synthesis of esters 5q-u from aldehydes 3n-p without oxidizing primary alcohol present in the substrate.