78168-74-8Relevant academic research and scientific papers
An Enzymatic Platform for Primary Amination of 1-Aryl-2-alkyl Alkynes
Liu, Zhen,Qin, Zi-Yang,Zhu, Ledong,Athavale, Soumitra V.,Sengupta, Arkajyoti,Jia, Zhi-Jun,Garcia-Borràs, Marc,Houk,Arnold, Frances H.
supporting information, p. 80 - 85 (2022/01/08)
Propargyl amines are versatile synthetic intermediates with numerous applications in the pharmaceutical industry. An attractive strategy for efficient preparation of these compounds is nitrene propargylic C(sp3)-H insertion. However, achieving this reacti
Microwave-Assisted Palladium-Catalyzed Reductive Cyclization/Ring-Opening/Aromatization Cascade of Oxazolidines to Isoquinolines
Xu, Xianjun,Feng, Huangdi,Van Der Eycken, Erik V.
supporting information, p. 6578 - 6582 (2021/09/02)
An efficient palladium-catalyzed reaction of N-propargyl oxazolidines for the construction of 4-substituted isoquinolines under microwave irradiation is developed. This transformation proceeds through a sequential palladium-catalyzed reductive cyclization/ring-opening/aromatization cascade via C-O and C-N bond cleavages of the oxazolidine ring. The practical value of this method has also been explored by conducting a millimole-scale reaction, as well as by transforming the isoquinoline into a key intermediate for the synthesis of a lamellarin analogue.
Atom-Economical Cross-Coupling of Internal and Terminal Alkynes to Access 1,3-Enynes
Liu, Mingyu,Tang, Tianhua,Apolinar, Omar,Matsuura, Rei,Busacca, Carl A.,Qu, Bo,Fandrick, Daniel R.,Zatolochnaya, Olga V.,Senanayake, Chris H.,Song, Jinhua J.,Engle, Keary M.
supporting information, p. 3881 - 3888 (2021/04/06)
Selective carbon-carbon (C-C) bond formation in chemical synthesis generally requires prefunctionalized building blocks. However, the requisite prefunctionalization steps undermine the overall efficiency of synthetic sequences that rely on such reactions, which is particularly problematic in large-scale applications, such as in the commercial production of pharmaceuticals. Herein, we describe a selective and catalytic method for synthesizing 1,3-enynes without prefunctionalized building blocks. In this transformation several classes of unactivated internal acceptor alkynes can be coupled with terminal donor alkynes to deliver 1,3-enynes in a highly regio- and stereoselective manner. The scope of compatible acceptor alkynes includes propargyl alcohols, (homo)propargyl amine derivatives, and (homo)propargyl carboxamides. This method is facilitated by a tailored P,N-ligand that enables regioselective addition and suppresses secondary E/Z-isomerization of the product. The reaction is scalable and can operate effectively with as low as 0.5 mol % catalyst loading. The products are versatile intermediates that can participate in various downstream transformations. We also present preliminary mechanistic experiments that are consistent with a redox-neutral Pd(II) catalytic cycle.
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
Synthesis of 3-Keto Pyridines from the Conjugated Allenone – Alkynylamine Oxidative Cyclization Catalyzed by Supported Au Nanoparticles
Fragkiadakis, Michael,Kidonakis, Marios,Stratakis, Manolis,Zorba, Leandros
supporting information, p. 964 - 968 (2020/01/28)
Recyclable supported Au nanoparticles on TiO2 catalyze the cyclization of N-propargyl or N-homopropargyl β-enaminones followed by dehydrogenation (aromatization) leading to substituted 3-keto pyridines or 4-picolines in very good yields. This pathway is in contrast to their known cyclization in the presence of Au(I) or Au(III) catalysts which provides 1,4-oxazepines, instead. The enaminones are formed in situ upon mixing a conjugated allenone or allenyl ester with the alkynylamine, thus the pyridine-forming transformation is typically a one pot process. (Figure presented.).
Benzene-1,3,5-triyl Triformate (TFBen)-Promoted Palladium-Catalyzed Carbonylative Synthesis of 2-Oxo-2,5-dihydropyrroles from Propargyl Amines
Ying, Jun,Le, Zhengjie,Wu, Xiao-Feng
supporting information, p. 194 - 198 (2020/01/03)
In this letter, we developed a palladium-catalyzed procedure for the cyclocarbonylation of propargyl amines. Benzene-1,3,5-triyl triformate (TFBen) has been explored as the CO source and also as the key promotor. Various substituted 2-oxo-dihydropyrroles were produced in a facile manner in good yields (up to 90%).
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.
One-Pot Copper-Catalyzed Cascade Bicyclization Strategy for Synthesis of 2-(1H-Indol-1-yl)-4,5-dihydrothiazoles and 2-(1H-Indol-1-yl)thiazol-5-yl Aryl Ketones with Molecular Oxygen as an Oxygen Source
Xie, Jialin,Guo, Zhonglin,Huang, Yuanqiong,Qu, Yi,Song, Hongjian,Song, Haibin,Liu, Yuxiu,Wang, Qingmin
supporting information, p. 490 - 495 (2019/01/04)
An atom-economical method for synthesizing N-heterocyclic indoles from readily available o-alkynylphenyl isothiocyanates and propargylamine derivatives is reported. This method involves a copper-catalyzed cascade bicyclization process consisting of an int
