279673-53-9

Upstream product

• 5029-67-4 2-iodopyridine 
• 38846-64-9 2-ethynylbenzaldehyde 
• 77123-58-1 2-[2-(trimethylsilyl)ethynyl]benzaldehyde 
• 1945-84-2 2-ethynylpyridine 
• 6630-33-7 ortho-bromobenzaldehyde 

Downstream Products

• 452094-06-3 2-(2-pyridin-2-ylethynyl)benzyl alcohol 
• 947395-66-6 2-pyridin-2-ylethynyl-benzylazide 
• 452094-20-1 C₅H₄NCHCSn(C₄H₉)3C₆H₄(o-CHO) 
• 1361106-93-5 C₂₁H₁₇N₃O₂S 
• 14243-64-2 (triphenylphosphine)gold(I) chloride 

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.

Transition-Metal-Free Reverse Reactivity of (2-Alkynyl)-Arylaldimines: Assembly of Functionalized Amino-Indinones

Transition-metal-free regioselective synthesis of functionalized amino-indenones by the reaction of ortho-alkynylaldehydes with a broad range of primary amines by intramolecular cyclization has been described. The designed reaction proceeds through KOH-mediated Prins-type cyclization and DMSO-promoted oxidation of the cyclopent-2-en-1-one system. The proposed mechanism and role of solvent were well supported by control experiments. For the first time, we have disclosed the reverse reactivity of (2-alkynyl)-arylaldimines in a super basic system.

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.).

Silver-Catalysed Domino Approach to 1,3-Dicarbo-Substituted Isochromenes

We report herein the first example of the silver triflate catalysed synthesis of 1,3-dicarbo-substituted isochromene derivatives starting from 2-alkynyl(hetero)arylaldehydes and enolizable ketones. The reaction proceeds in a cascade fashion under mild heating with complete regioselectivity and moderate-to-good yields. In some cases, the reaction gives unexpected homodimeric products. Two competitive mechanistic paths for the formation of the desired isochromene derivatives and the homodimeric products are described.

Gold-Catalyzed Ring Expansion of Enyne-Lactone: Generation and Transformation of 2-Oxoninonium

An efficient gold-catalyzed ring-expansion reaction of enyne-lactones to form 2-oxoninonium intermediates is reported. The 2-oxoninonium generated in this work could undergo further 6π electrocyclization and aromatization reaction to produce different aromatic compounds.

Radical Cascade Cyclization: Reaction of 1,6-Enynes with Aryl Radicals by Electron Catalysis

The radical cascade cyclization of various 1,6-enynes with aryl radicals by electron catalysis under metal-free reaction conditions was explored. Readily available anilines were used as radical precursors, and the reactions proceeded in the absence of any transition metal. These cascades comprise three C–C bond formations, which provide polycyclic structures with extended π-systems. The photophysical properties of some of these novel compounds were investigated, and a plausible reaction mechanism is proposed.

Bioinspired intramolecular diels-alder reaction: A rapid access to the highly-strained cyclopropane-fused polycyclic skeleton

A bioinsipred gold-catalyzed tandem Diels-Alder/Diels-Alder reaction of an enynal and a 1,3-diene, forming the highly-strained benzotricyclo[3.2.1.0 2,7]octane skeleton, was reported. In contrast, a Diels-Alder/Friedel-Crafts tandem reaction occurred instead when silver salts were used as the catalyst. Although both reactions experienced the similar Diels-Alder reaction of a pyrylium intermediate with a 1,3-diene, they have different reaction mechanisms. The former proceeded with a stepwise Diels-Alder reaction, while the latter one with a concerted one. Mother nature knows best! A gold-catalyzed reaction of enynals and 1,3-dienes, giving rapid access to the highly strained benzotricyclo[3.2.1.02,7]octane skeleton, is reported (see scheme; QMD=quinodimethane). Owing to the mild reaction conditions, excellent substrate scope, and high functional-group tolerance, this system holds potential for the construction of complex molecules with the tricyclo[3.2.1.02,7]octane skeleton. Copyright

Gold-catalyzed reactions of enynals/enynones with norbornenes: Generation and trapping of cyclic o-quinodimethanes (o-QDMs)

Fan-like structures: An efficient AuIII-catalyzed method to generate the highly reactive cyclic o-quinodimethane (o-QDM) species from easily available enynals or enynones is presented (see scheme). This method produced a variety of structurally unique fan-like products with the advantages of mild reaction conditions, excellent diastereoselectivities, and high functional-group tolerance. Copyright

Aryne [3 + 2] cycloaddition with N-sulfonylpyridinium imides and in situ generated N-sulfonylisoquinolinium imides: A potential route to pyrido[1,2-b]indazoles and indazolo[3,2-a]isoquinolines

The aryne [3 + 2] cycloaddition process with pyridinium imides breaks the aromaticity of the pyridine ring. By equipping the imide nitrogen with a sulfonyl group, the intermediate readily eliminates a sulfinate anion to restore the aromaticity, leading to the formation of pyrido[1,2-b]indazoles. The scope and limitation of this reaction are discussed. As an extension of this chemistry, N-tosylisoquinolinium imides, generated in situ from N′-(2-alkynylbenzylidene)-tosylhydrazides via an AgOTf-catalyzed 6-endo-dig electrophilic cyclization, readily undergo aryne [3 + 2] cycloaddition to afford indazolo[3,2-a]-isoquinolines in the same pot, offering a highly efficient route to these potential anticancer agents.

Synthesis of 1,3,4-trisubstituted isoquinolines by iodine-mediated electrophilic cyclization of 2-alkynyl benzyl azides

(Chemical Equation Presented) The I's have it: A series of 2-alkynyl benzyl azides have been smoothly converted into 1,3,4-trisubstituted isoquinolines in moderate to excellent yields by an iodonium-mediated synthesis (see scheme). Depending on the struct