7404-46-8Relevant academic research and scientific papers
Continuous Flow Magnesiation or Zincation of Acrylonitriles, Acrylates, and Nitroolefins. Application to the Synthesis of Butenolides
Ganiek, Maximilian A.,Becker, Matthias R.,Ketels, Marthe,Knochel, Paul
, p. 828 - 831 (2016)
Scalable continuous flow procedures are reported for the metalation and downstream functionalization of β-substituted acrylates. The flow conditions allow the metalation of acrylonitriles, acrylates, and nitroolefins at 0.25-2.50 mmol/min conversion rates. Magnesiations can be performed with short residence times (1-20 min) and near-ambient temperature using TMPMgCl·LiCl. Further, high temperature zincation (≤90°C) using TMPZnCl·LiCl is possible. This method allows a simple entry to 2(5H)-furanones by flow generation of magnesiated acrylates and a subsequent reaction with aldehydes. (Chemical Equation Presented).
Rhodium(I)-Catalyzed CO-Gas-Free Arylative Dual-Carbonylation of Alkynes with Arylboronic Acids via the Formyl C-H Activation of Formaldehyde
Morimoto, Tsumoru,Wang, Chuang,Tanimoto, Hiroki,Artok, Levent,Kakiuchi, Kiyomi
, p. 3372 - 3382 (2021/05/04)
The rhodium(I)-catalyzed reaction of alkynes with aryl boronic acids in the presence of formaldehyde results in a CO-gas-free arylative dual-carbonylation to produce γ-butenolide derivatives. The simultaneous loading of phosphine-ligated and phosphine-free rhodium(I) complexes is required for efficient catalysis. The former complex catalyzes the abstraction of a carbonyl moiety from formaldehyde through the activation of its formyl C-H bond (decarbonylation) and the latter catalyzes the subsequent dual-incorporation of the resulting carbonyl unit (carbonylation). The use of larger amounts of the phosphine-ligated rhodium(I) complex generates more carbonyl units, leading to the formation γ-butenolides via the dual-incorporation of the carbonyl unit.
Titanium-Promoted Cross-Coupling for the Selective Synthesis of Polysubstituted, Conjugated Amides
Chenniappan, Vinoth Kumar,Rahaim, Ronald J.
supporting information, p. 5090 - 5093 (2016/10/14)
α,β-Unsaturated amides are important building blocks and are key structural elements in a number of biologically active natural products. Despite their importance and prevalence, few methods exist to prepare conjugated amides directly and modularly. To address this gap, a titanium-promoted coupling of alkynes and isocyanates has been developed. The method is highly stereoselective, producing only the E isomer with good chemoselectivity and regioselectivity (>95/5), for unsymmetrical internal alkynes that contain a steric bias. The reactive titanacyclopentene intermediate formed from the coupling of the alkyne and isocyanate was additionally reacted with various electrophiles to access tetrasubstituted enamides.
Intermolecular [2+2+1] Carbonylative Cycloaddition of Aldehydes with Alkynes, and Subsequent Oxidation to γ-Hydroxybutenolides by a Supported Ruthenium Catalyst
Miura, Hiroki,Takeuchi, Kazuki,Shishido, Tetsuya
supporting information, p. 278 - 282 (2016/01/25)
Intermolecular [2+2+1] carbonylative cycloaddition of aldehydes with alkynes and subsequent oxidation to γ-hydroxybutenolides is achieved using a supported ruthenium catalyst. A ceria-supported ruthenium catalyst promotes the reaction efficiently, even with an ambient pressure of CO or without external CO, thus giving the corresponding γ-hydroxybutenolide derivatives in good to high yields. Moreover this catalyst can be reused with no loss of activity.
Nickel(0)-catalyzed formation of oxaaluminacyclopentenes via an oxanickelacyclopentene key intermediate: Me2AlOTf-assisted oxidative cyclization of an aldehyde and an alkyne with nickel(0)
Ohashi, Masato,Saijo, Hiroki,Arai, Tomoya,Ogoshi, Sensuke
experimental part, p. 6534 - 6540 (2011/02/17)
The use of Me2AlOTf as an additive allowed the oxidative cyclization of pivalaldehyde and diphenylacetylene with nickel(0) in the presence of PCy3 to give an oxanickelacyclopentene, the structure of which was unambiguously determined
Rhodium catalyzed reaction of internal alkynes with organoborons under CO atmosphere: a product tunable reaction
Artok, Levent,Ku?, Melih,Aksin-Artok, ?zge,Dege, Fatma Nurcan,?zkilin?, Fatma Yelda
scheme or table, p. 9125 - 9133 (2010/01/16)
Alkynes react with organoborons under a CO atmosphere in the presence of a rhodium(I) catalyst to afford mainly 5-aryl-2(5H)-furanones, α,β-unsaturated ketones, and indanones. The product selectivity can be tuned by modifying the reaction conditions.
Synthesis of α,β-unsaturated ketones by rhodium-catalyzed carbonylative arylation of internal alkynes with arylboronic acids
Ku?, Melih,Artok, ?zge Aksin,Ziyanak, Firat,Artok, Levent
experimental part, p. 2587 - 2592 (2009/04/16)
The Rh-catalyzed reaction of arylboronic acids with internal alkynes under a CO atmosphere in the presence of an acid additive afforded α,β-unsaturated ketones as the major products. Hydroacylation of internal alkynes, except in the case of diaryl acetylenes, proceeded in syn fashion, yielding the E-configured isomer. A mixture of E- and Z-isomers was obtained with diphenyl acetylene. Reactions were also highly regioselective for various nonsymmetric alkynes.
Rhodium-catalyzed carbonylative arylation of alkynes with arylboronic acids: An efficient and straightforward method in the synthesis of 5-aryl-2(5H)-furanones
Aksin, Oezge,Dege, Nurcan,Artok, Levent,Tuerkmen, Hayati,Cetinkaya, Bekir
, p. 3187 - 3189 (2008/09/19)
5-Aryl-2(5H)-furanones can be synthesized by the Rh-catalyzed reactions of arylboronic acids with internal alkynes under a CO atmosphere. The Royal Society of Chemistry 2006.
Acylpalladation of internal alkynes and palladium-catalyzed carbonylation of (Z)-β-iodoenones and related derivatives producing γ-lactones and γ-lactams
Copéret, Christophe,Sugihara, Takumichi,Wu, Guangzhong,Shimoyama, Izumi,Negishi, Ei-Ichi
, p. 3422 - 3431 (2007/10/02)
The reaction of either an internal alkyne-organic halide mixture or (Z)-β-iodoenones with CO in the presence of a Pd-phosphine catalyst, e.g., Cl2Pd(PPh3)2, can give one of the three discrete types of compounds as the major products depending on the substrate structure and the reaction conditions. Those substrates which are convertible to (Z)-γ-oxo-α,β-unsaturated acylpalladium derivatives lacking δ-H atoms are converted to the corresponding 2-butenolides (13) in the presence of water, which serves as a H donor. Carbon monoxide most likely is the source of two electrons. Either in the absence of water (or any other suitable H source) or in the presence of some factors disfavoring the butenolide formation, the same reaction gives the corresponding dimeric product (16). Even in cases where there is an α-H atom in the α-substitutent, 1,4-elimination products (11), reported to be the major products in a related Pd-catalyzed reaction of terminal alkyne-aryl iodide mixtures with CO, were not detected. In sharp contrast, those substrates which can give rise to (Z)-γ-oxo-α,β-unsaturated acylpalladium derivatives containing δ-H atoms give, under comparable reaction conditions, enol lactones (12), i.e., (Z)-3-alkylidene-2-butenolides, contaminated with only very minor amounts of 22 even in cases where an excess (4 equiv) of water was present. The required (Z)-β-iodoenones can be readily prepared in one pot via ZrCp2-promoted cyclization of alkynes with nitriles. The ready availability of the starting compounds and the high Z stereoselectivity make the overall sequence an attractive synthetic route to 12. The courses of the Pd-catalyzed carbonylation reactions of (Z)-β-iodo-α,β-unsaturated imines 23 closely parallel the reactions of enones and produce the corresponding lactams, i.e., 24 and 25.
Substituent Effects in the Photochemistry of 5-Aryl-3,3-diphenyl-2(3H)-furanones. Steady-State and Laser Flash Photolysis Studies
Pratapan, S.,Ashok, K.,Cyr, D.R.,Das, P.K.,George, M.V.
, p. 5826 - 5831 (2007/10/02)
The photochemistry of a series of 5-aryl-3,3-diphenyl-2(3H)-furanones, containing electron-releasing as well as electron-withdrawing para substituents on the phenyl group at theC5 position, has been investigated by steady-state photolysis, prod
