4656-94-4Relevant academic research and scientific papers
Autotandem Catalysis: Inexpensive and Green Access to Functionalized Ketones by Intermolecular Iron-Catalyzed Amidoalkynylation/Hydration Cascade Reaction via N-Acyliminium Ion Chemistry
Abdallahi, Sidi Mohamed,Ewies, Ewies F.,El-Shazly, Mohamed,Ould Elemine, Brahim,Hadou, Abderrahmane,Moncol, Ján,Lawson, Ata Martin,Daich, Adam,Othman, Mohamed
supporting information, p. 15440 - 15449 (2021/10/07)
Iron-based catalysts were applied in cascade-type reactions for the synthesis of different carbonyl compounds. The reactions proceeded by a new iron-catalyzed cascade of alkynylation/hydration by using both the σ- and π-Lewis acid properties of iron salts. The alkynylation reactions of several endo and exocyclic acetoxylactams were achieved with three different catalysts including FeCl3 ? 6H2O, FeCl3, and Fe(OTf)3 showing the efficiency of σ-Lewis acidity of iron (III) salts in catalyzing the alkynylation reaction. We also demonstrated that the reaction sequence could be shortened by the direct use of hydroxylactams, leading to an environmentally friendly protocol, avoiding the need to perform unnecessary lengthy steps. A combination of the hard/soft iron Lewis acid properties was then used to implement an unprecedented tandem intermolecular alkynylation/intramolecular hydration sequence allowing expedient access to a new carbonyl structures from trivial materials.
Gold-Catalyzed Regioselective Oxyfluorination/Oxydifluorination vs. Diketonization of Phthalimido-Protected Propargylamines with Selectfluor
Arcadi, Antonio,Marsicano, Vincenzo,Michelet, Véronique
supporting information, (2022/01/22)
Alkyl- and aryl-substituted N-propargyl phthalimides were used as valuable building blocks for the selective formation of the corresponding α-fluoro, β-phthalimido ketones, α,α-difluoro, β-phthalimido ketones or β-phthalimido α-diketones by means of gold-catalyzed oxyfluorination/oxydifluorination or dioxygenation reactions. The key factors addressing the product selectivity control were determined. The simultaneous assembly of the quinoxaline nucleus and the removal of the phthalimido-protecting group were tested. Reaction mechanisms of the different reaction pathways are assumed.
Cobalt-Catalyzed Regioselective Carboamidation of Alkynes with Imides Enabled by Cleavage of C-N and C-C Bonds
Chen, Bing-Zhi,Chen, Qing-An,Hu, Yan-Cheng,Ji, Ding-Wei,Min, Xiang-Ting,Wan, Boshun,Zheng, Hao
, p. 3386 - 3391 (2020/04/20)
Through the oxidative addition of cobalt into the N-C(O) bond of phthalimide and the subsequent decarbonylation, we describe an efficient cobalt-catalyzed intermolecular decarbonylative carboamidation of alkynes. High regioselectivities have been achieved for unsymmetrical alkynes (including aryl-alkyl or aryl-aryl) to deliver polysubstituted isoquinolones. To facilitate step economy, a three-component decarbonylative carboamidation of alkynes with phthalic anhydrides and amines has been demonstrated using the current cobalt catalysis.
Experimental and computational evidence on gold-catalyzed regioselective hydration of phthalimido-protected propargylamines: An entry to β-amino ketones
Arcadi, Antonio,Aschi, Massimiliano,Marsicano, Vincenzo,Michelet, Véronique
supporting information, p. 9438 - 9447 (2020/12/15)
The results of our investigations on the Au-catalyzed regioselective hydration reaction of both alkyl- A nd aryl-substituted N-propargyl phthalimides directed to the selective formation of the corresponding β-phthalimido ketones are described. Experimental data, in particular the observed regioselectivity, have been qualitatively supported by quantum-chemical calculations carried out on model systems in the framework of Density Functional Theory (DFT) followed by quantum theory of atoms in molecules (QTAIMS). Our results suggest that the electronic features of the initial adduct between the propargyl triple bond and the Au(i) catalyst, in particular the character of the gold-triple bond interaction, are essential for the observed regioselectivity. Other effects, such as the presence of the solvent and the formation of a H-bond between the water molecule and the phthalimido moiety, although apparently irrelevant for the regioselectivity, have proven to be kinetically and catalytically rather important. This journal is
Tandem Thioacylation-Intramolecular Hydrosulfenylation of Propargyl Amines – Rapid Access to 2-Aminothiazolidines
Singh, Ravi P.,Gout, Delphine,Lovely, Carl J.
, p. 1726 - 1740 (2019/02/24)
An investigation directed towards the preparation of α-substituted propargyl thioureas from the corresponding propargylamine resulted in a tandem thioacylation/anti-hydrosulfenylation and the formation of the corresponding thiazolidine in excellent (46–98
Novel thiazolidines: Synthesis, antiproliferative properties and 2D-QSAR studies
Singh, Ravi P.,Aziz, Marian N.,Gout, Delphine,Fayad, Walid,El-Manawaty, May A.,Lovely, Carl J.
, (2019/08/30)
A series of N-substituted (Z)-2-imino-(5Z)-ylidene thiazolidines/thiazolidin-4-ones were synthesized and their antiproliferative activities against colon (HCT-116) and breast (MCF7) cancer cell lines were evaluated utilizing an MTT growth assay. A 2D-QSAR investigation was conducted to probe and validate the obtained antiproliferative properties for the thiazolidine derivatives. The majority of the thiazolidines exhibit higher potency against a colon cancer cell line relative to the standard reference. The p-halophenylimino p-anisylidene derivatives exhibited the highest anti-proliferative activity against HCT116 relative to control (IC50 = 8.9–10.0 μM compared to 20.4 μM observed for 5-fluorouracil as positive control). An X-ray study confirmed the Z, Z′-configurations for two examples of the synthesized compounds.
Arene Trifunctionalization with Highly Fused Ring Systems through a Domino Aryne Nucleophilic and Diels–Alder Cascade
He, Jia,Jia, Zizi,Tan, Hongcheng,Luo, Xiaohua,Qiu, Dachuan,Shi, Jiarong,Xu, Hai,Li, Yang
supporting information, p. 18513 - 18518 (2019/11/19)
A convenient and efficient domino aryne process was developed under transition-metal-free conditions to generate a range of tetra- and pentacyclic ring systems. This transformation was realized via a 1,2-benzdiyne through a nucleophilic and Diels–Alder reaction cascade using styrene as the diene moiety. Three new chemical bonds, namely one C?N and two C?C bonds, and two benzofused rings could be constructed concomitantly, which was made possible by distinct chemoselective control at both the 1,2-aryne and 2,3-aryne stages. Moreover, in-depth studies were carried out on the domino aryne precursors and controlling the diastereoselectivity.
Silver-Catalyzed Synthesis of Substituted Pyridine Derivatives from N-Propargylic α-Enamino Esters
Sakthivel, Shanmugam,Sharma, Ashish,Balamurugan, Rengarajan
supporting information, p. 3941 - 3946 (2017/07/28)
A wide range of substituted pyridine derivatives were synthesized in moderate to good yields from N-propargylic α-enamino esters. The synthetic strategy involved regioselective addition of a propargylamine to the α-carbon atom of an alkynyl ester to produce the N-propargylic α-enamino ester, which acted as the key intermediate in the synthesis.
Preparation of 1,2,5-Trisubstituted 1H-Imidazoles from Ketenimines and Propargylic Amines by Silver-Catalyzed or Iodine-Promoted Electrophilic Cyclization Reaction of Alkynes
Zhou, Xiaorong,Jiang, Zheng,Xue, Lexing,Lu, Ping,Wang, Yanguang
supporting information, p. 5789 - 5797 (2015/09/15)
From readily available propargylic amines, 1,2,5-trisubstituted imidazoles are efficiently obtained through a cascade reaction catalyzed by AgOTf or promoted by molecular iodine. The AgOTf-catalyzed reaction involves nucleophilic addition of propargylic amine to ketenimine, a silver-catalyzed electrophilic cyclization reaction of alkyne, and a tautomerism/isomerism/metal-H exchange cascade. The iodine-mediated counterpart yields 5-formyl-1,2-disubtituted imidazoles, which presumably includes a cascade hydrolysis/oxidation reaction. Furthermore, the presented protocol can be scaled up and the resultant 1,2,5-trisubstituted imidazole can be converted into fused indeno[1,2-d]imidazole. 1,2,5-Trisubstituted imidazoles are efficiently prepared from readily available propargylic amines through a AgOTf-catalyzed or molecular iodine-promoted cascade reaction. The presented protocol can be scaled up and the resultant 1,2,5-trisubstituted imidazoles can be converted into fused indeno[1,2-d]imidazoles.
Palladium-catalyzed oxidative carbonylative coupling of arylboronic acids with terminal alkynes to alkynones
Natte, Kishore,Chen, Jianbin,Neumann, Helfried,Beller, Matthias,Wu, Xiao-Feng
supporting information, p. 5590 - 5593 (2014/07/22)
We describe here an interesting palladium-catalyzed oxidative carbonylation of arylboronic acids with terminal alkynes. By the appropriate combination of a palladium salt, a ligand, and an oxidant, the desired alkynones were isolated in moderate to good yields. Notably, all the reactions were performed at room temperature, and moisture and air can be tolerated by this procedure. More importantly, this is the first example of oxidative carbonylative coupling of arylboronic acids with alkynes which filled the missing link in carbonylative coupling reactions. the Partner Organisations 2014.
