223553-44-4

Upstream product

• 159087-45-3 4,4,5,5-tetramethyl-2-phenylethynyl-[1,3,2]dioxaborolane 
• 57134-53-9 3,4-methylenedioxyphenylethyne 
• 7507-86-0 2-bromo-5-methoxy-benzaldehyde 
• 150192-39-5 2-Bromo-5-methoxybenzyl alcohol 
• 1205555-48-1 [5-methoxy-2-(2-phenylethynyl)phenyl]methanol 
• 139557-96-3 (2-iodo-5-methoxyphenyl)methanol 
• 536-74-3 phenylacetylene 
• 424788-79-4 trifluoro-methanesulfonic acid 2-formyl-4-methoxy-phenyl ester 

Downstream Products

• 1186603-46-2 C₁₆H₁₆O₂ 
• 14963-94-1 7-methoxy-3-phenyl-1H-isochromen-1-one 
• 1421694-57-6 5-methoxy-2-(2-oxo-2-phenylethyl)benzaldehyde 
• 1389315-69-8 2-benzyl-4-bromo-7-methoxy-3-phenylisoquinolin-1(2H)-one 
• 1391921-33-7 2-(2,2-dibromovinyl)-4-methoxy-1-(phenylethynyl)benzene 

Relevant academic research and scientific papers

Catalytic Asymmetric Tandem Reaction of o-Alkynylbenzaldehydes, Amines, and Diazo Compounds

An efficient asymmetric tandem reaction of o-alkynylbenzaldehydes, amines, and diazo compounds catalyzed by chiral silver imidodiphosphate has been established. Chiral 1,2-dihydroisoquinoline analogues have a tertiary stereocenter at the C1 position, and substituents at the C3 position are available with up to 97% yields and 98% ee. These products can be elaborated into the corresponding β-aminophosphonates or PARP1-inhibitor analogues.

Br?nsted/Lewis Acid-Promoted Site-Selective Intramolecular Cycloisomerizations of Aryl-Fused 1,6-Diyn-3-ones for Diversity-Oriented Synthesis of Benzo-Fused Fluorenes and Fluorenones and Naphthyl Ketones

Herein, a facile diversity-oriented approach to access functionalized benzo[a]fluorenes, benzo[b]fluorenones, and naphthyl ketones has been demonstrated via site-selective intramolecular cyclization of aryl-fused 1,6-diyn-3-ones. Synthesis of benzo[a]fluorenes and naphthyl ketones has been achieved selectively using TfOH and AgBF4, respectively, via in situ-formed acetals. Aryl-fused 1,6-diyn-3-ones undergo triflic acid-mediated intramolecular cyclization, leading to benzo[b]fluorenone derivatives via a radical intermediate as supported by EPR studies. Kinetic studies of these transformations have also been performed by UV-visible spectroscopic analysis to shed light on the reaction profile.

Tunable Synthesis of Indeno[1,2- c]furans and 3-Benzoylindenones via FeCl3-Catalyzed Carbene/Alkyne Metathesis Reaction of o-Alkynylbenzoyl Diazoacetates

An efficient synthesis of indeno[1,2-c]furan and 3-benzoylindenone derivatives through a FeCl3-catalyzed carbene/alkyne metathesis reaction of o-alkynylbenzoyl diazoacetates is presented. Mechanistically, the key intermediate, vinyl iron carbene, is formed by 5-exo-dig carbocyclization and terminated with a formal [3 + 2] cycloaddition or carbonylation. To the best of our knowledge, this is the first example in which FeCl3 is used as a catalyst for a carbene/alkyne metathesis reaction. Finally, derivatization reactions were carried out to showcase the value of the products.

Synthesis of N-(isoquinolin-1-yl)sulfonamides via Ag2O-catalyzed tandem reaction of ortho-alkynylbenzaldoximes with benchtop stabilized ketenimines

In this project, a moderately efficient approach to multisubstituted N-(isoquinolin-1-yl)sulfonamide derivatives was illustrated, utilizing ortho-alkynylbenzaldoximes and zwitterionic ketenimine salts in a tandem reaction catalyzed by silver oxide. The oxophilicity of Ag2O, along with its nature as Lewis acid, pave the way for a smooth [3 + 2] cycloaddition between isoquinoline N-oxides and ketenimine species, which is a key step in this reaction. DFT calculation suggests that 1,3-dipolar cycloaddition of nitrone and ketenimine proceeds through a selective stepwise mechanism.

Single Cu(I)-Photosensitizer Enabling Combination of Energy-Transfer and Photoredox Catalysis for the Synthesis of Benzo[ b]fluorenols from 1,6-Enynes

An efficient, mild, and atom-economical synthesis of benzo[b]fluorenols from 1,6-enynes has been developed under photocatalytic conditions. A single P/N heteroleptic Cu(I)-photosensitizer might exhibit both energy-transfer and photoredox catalytic activities in the formation of benzo[b]fluorenols.

Modular synthesis of 3-substituted isocoumarinsviasilver-catalyzed aerobic oxidation/6-endoheterocyclization ofortho-alkynylbenzaldehydes

A method involving silver-catalyzed aerobic oxidation/6-endoheterocyclization ofortho-alkynylbenzaldehydes to yield 3-substituted isocoumarins is described. The developed protocol allows convenient access to a range of synthetically useful 3-substituted isocoumarins and related fused heterocyclolactones in good to high yields, using silver tetrafluoroborate as the catalyst, and atmospheric oxygen as the terminal oxidant and the source of endocyclic oxygen. Mechanistic studies suggest the involvement of a free-radical pathway.

Polarization Effect on Regioselectivity of Pd-Catalyzed Cyclization of 2-Alkynylbenzaldehydes

We report a study on the relationship between the polarization of C≡C bond in a series of 2-alkynylbenzaldehydes and the regioselectivity of their Pd-catalyzed annulation reactions. The electrophilic and nucleophilic character of the triple bond carbon atoms was examined using 13C and HMBC NMR experiments. The direction of polarization is determined only by the formyl group and its position on an aromatic ring. On the other hand, the strength of the polarization expressed through chemical shift difference Δδ of acetylenic carbon atoms is a result of electron-withdrawing or electron-donating ability of the other substituent. Out of two possible regioisomers, the Pd-catalyzed cyclization reactions of 2-alkynylbenzaldehydes that were studied predominantly afforded 1H-isochromenes suggesting that the polarization of a triple bond is one of the contributing factors in the regioselectivity of this process.

Palladium-catalyzed cascade decarboxylative amination/6- endo-dig benzannulation of o-alkynylarylketones with n-hydroxyamides to access diverse 1-naphthylamine derivatives

An efficient and practical one-pot strategy to produce highly substituted 1-naphthylamines via sequential palladium-catalyzed decarboxylative amination/intramolecular 6-endo-dig benzannulation reactions has been described. In this reaction, a broad range of electron-rich, electron-neutral, and electron-deficient o-alkynylarylketones react well with N-hydroxyl aryl/alkylamides to give a diversity of 1-naphthylamines in good to excellent yields under mild reaction conditions. The gram-scale synthesis, with benefits such as undiminished product yield and easy transformation, illustrated the practicality of this method.

Catalytic asymmetric three-component reaction of 2-alkynylbenzaldehydes, amines, and dimethylphosphonate

An efficient enantioselective synthesis of cyclic α-aminophosphonates via multicomponent reactions of 2-alkynylbenzaldehydes, amines, and dimethylphosphonate has been developed with the use of a chiral silver spirocyclic phosphate as the catalyst. This protocol provides straightforward access to a series of chiral C1-phosphonylated 1,2-dihydroisoquinoline derivatives with high yields (up to 99%) and high enantioselectivities (up to 94% ee) for a broad substrate scope. The products could be further transformed into densely functionalized compounds and corresponding α-aminophosphonic acids.

Synthesis of organoselenyl isoquinolinium imidesviairon(iii) chloride-mediated tandem cyclization/selenation ofN′-(2-alkynylbenzylidene)hydrazides and diselenides

This report describes the synthesis of organoselenyl isoquinolinium imides through a tandem cyclization betweenN′-(2-alkynylbenzylidene)hydrazides and diselenides. The reaction was carried out at room temperature under an ambient atmosphere using cheap iron(iii) chloride as the metallic source. The strategy shows good tolerance to a broad range ofN′-(2-alkynylbenzylidene)hydrazides and diselenides, and forms C-N and C-Se bonds in one step. The obtained product is further transformed into a bioactiveH-pyrazolo[5,1-a]isoquinoline skeleton easilyviaa silver catalyzed [3 + 2] cycloaddition.