91620-99-4

Upstream product

• 762-21-0 acetylenedicarboxylic acid diethyl ester 
• 762-42-5 dimethyl acetylenedicarboxylate 
• 88284-48-4 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 
• 107-05-1 3-chloroprop-1-ene 
• 75-03-6 ethyl iodide 
• 67-56-1 methanol 
• 64-17-5 ethanol 
• 517-60-2 benzenehexacarboxylic acid 

Relevant academic research and scientific papers

Palladium-catalyzed controlled carbopalladation of benzyne

2-Trimethylsilylphenyl trifluoromethanesulfonate 1a, a benzyne precursor, reacted with the allylic chlorides 2a - f in the presence of CsF (2.0 equiv) and Pd2(dba)3·CHCl3 (2.5 mol %)-dppf (5 mol %) in a 1:1 mixed solvent of CH3CN and THF to produce the phenanthrene derivatives 3 along with their minor regioisomers 4 in good yields (i) and the reaction of 1a with 2a and the internal alkynes 15a,c - e afforded the naphthalene derivatives 16 in moderate yields (ii). The reaction of benzyne precursor 1a with the alkynes 15a - c,f - h in the presence of Pd(OAc)2 (5 mol %)-(o-tolyl)3P (5 mol %) catalyst and CsF (2.0 equiv) in CH3CN gave the phenanthrene derivatives 17 (iii), whereas the reaction of 1a with the alkynes 15a,b,i in the presence of the same catalysts and CsF in CH3CN - toluene gave the indene derivatives 18 in good yields (iv). Detailed mechanistic investigation revealed that the former two reactions i and ii proceed through carbopalladation to free benzyne, while the latter two reactions iii and iv proceed through the nonfree benzyne mechanism, in which the initial step of the catalytic cycle begins with Pd(0) insertion to the Ar - OTf bond of 1.

Exploration of [2 + 2 + 2] cyclotrimerisation methodology to prepare tetrahydroisoquinoline-based compounds with potential aldo-keto reductase 1C3 target affinity

Tetrahydroisoquinoline (THIQ) is a key structural component in many biologically active molecules including natural products and synthetic pharmaceuticals. Here, we report on the use of transition-metal mediated [2 + 2 + 2] cyclotrimerisation of alkynes to generate tricyclic THIQs with potential to selectively inhibit AKR1C3.

Reactivity of electron-deficient alkynes on gold nanoparticles

Propiolates cyclotrimerize in the presence of catalytic amounts of gold nanoparticles to give aryl benzoates in high yields and with turnover frequencies of thousands per hour. Types of alkynes other than propiolates do not react, and, if molecular oxygen

Efficient and regioselective nickel-catalyzed [2 + 2 + 2] cyclotrimerization of ynoates and related alkynes

A nickel-based catalytic system has been developed for [2 + 2 + 2] cyclotrimerization of various alkynes, especially ynoates. This catalytic system enables facile construction of substituted aromatic compounds in excellent yields with high regioselectivity. The Royal Society of Chemistry 2013.

Rhodium-catalyzed linear cross-trimerization of two different alkynes with an alkene and two different alkenes with an alkyne

Crossing paths with rhodium: A cationic RhI/H8-BINAP complex has been found to catalyze the linear cross-trimerization of terminal alkynes, acetylenedicarboxylates, and acrylamides to give substituted trienes. The asymmetric linear c

Efficient intermolecular [2 + 2 + 2] alkyne cyclotrimerization in aqueous medium using a ruthenium(IV) precatalyst

The dimeric bis(allyl)-ruthenium(IV) complex [{Ru(η3:η3-C10H16)(μ-Cl)Cl}2] (C10H16 = 2,7-dimethylocta-2,6-diene-1,8-diyl) was found to catalyze efficiently the [2 + 2 + 2] cyclization of terminal and internal alkynes in aqueous medium. Copyright

Rhodium-catalyzed tandem cyclization: Formation of 1H-indenes and 1-alkylideneindans from arylboronate esters in aqueous media

Arylboronate esters bearing a pendant Michael-type acceptor olefin or acetylene linkage undergo transmetalation with a rhodium-based catalytic complex to generate a functionalized organorhodium intermediate which can cyclize onto nonterminal acetylenes in

Reductive dimerization of dialkyl acetylenedicarboxylate catalyzed by [Rh(binap)(MeOH)2]ClO4 in methanol

Cationic Rh(I) complex [Rh(binap)(MeOH)2]ClO4 catalyzes reductive dimerization of dialkyl acetylenedicarboxylates 1 to give 1,2,3,4-tetrakis(alkoxycarbonyl)-1,3-butadienes 2 in methanol selectively.

Preparation, Properties, and Reactions of Metal-Containing Heterocycles, XC. Reactivity of Differently Activated Alkynes toward Ruthenium and Osmium Complexes of the Type (η2-C2H4)M(CO)4

Depending on the substituents, the reaction of the activated alkynes ZCCZ (2a-g) a), Et (b); Z = R1: R1 = CF3 (c), CH2Cl (d), CH2Br (e); Z = CH2OC(O)R2: R2 = Me (f), CCl3 (g)> with the labile ruthenium complex (η2-C2H4)Ru(CO)4 (1) results in the formation of three different types of heterocycles.While the reactions of the dialkyl acetylenedicarboxylates 2a, b lead to the dimeric tricarbonylruthenacyclopentadienes 3a, b, being catalytically active in the cyclotrimerization of alkynes like 2a, b, the application of the 1,4-halogeno-2-butynes 2c-e yields the bicyclic heterocycles 4c-e.The esters of 2-butyne-1,4-diol 2f, g are converted into the tetracarbonylruthenacyclopentadienes 5f, g.Investigation of the primary attack of the alkynes 2a-g at complex 1 leads to the conclusion, that an ionic mechanism is preferred in the ruthenium-catalyzed cyclotrimerization of electron-poor alkynes.If, instead of 1, (η2-C2H4)Os(CO)4 (6) is allowed to react with acetylenes 2a, b the osmium complexes (η4-C6Z6)Os(CO)3 (7a, b) are isolated.In the presence of CO at 2 bar 7a, b release the benzene derivatives C6Z6 (8a, b) with the formation of Os3(CO)12. - Key Words: Ruthenium compounds / Osmium compounds / Alkynes, activated / Cyclotrimerization

Darstellung und Eigenschaften von und Reactionen mit metallhaltigen Heterocyclen. LXXII. Rutheniumhalgite Praekatalysatoren als Speicher fuer reaktive Zwischenstufen bei der katalytischen Cyclotrimerisierung von Alkinen

(η2-C2H4)Ru(CO)4 (1) reacts with the activated alkynes ZCCZ (2a-c, e, g) to give the tricyclic compounds 3a-c, e, g containing two tricarbonylruthenacyclopentadiene rings.The tendency of formation and the yield of 3a-c, e, g is dependent on the steric demand of the substituents R. 3a-c, e, g are precatalysts for the cyclotrimerization of 2a-c, e, g to the benzene derivatives 4a-c, e, g.In the same way 3a cyclotrimerizes 2b, c, e-h (2h: HCCCO2CH3) to 4b, c, e-h.