37696-01-8Relevant articles and documents
One-pot Sonogashira–Hydroarylation reaction catalyzed by anionic palladium complexes in an aqueous medium
Dziadas, M.,Trzeciak, A. M.,Wójcik, E.
supporting information, (2022/01/26)
It was found that anionic Pd(II) complexes of type [CA]2[PdCl4] and [CA]2[Pd2Cl6] (CA = imidazolium or pyridinium cation) are effective catalysts for copper-free Sonogashira coupling in an aqueous med
Simple and efficient diaryl alkyne synthesis method
-
Paragraph 0026; 0029-0031, (2021/04/14)
The embodiment of the invention discloses a simple and efficient diaryl alkyne synthesis method. The method comprises the steps of by taking arylmethylbenzotriazole and aromatic aldehyde as raw materials, carrying out addition and double-beta-elimination reaction under the action of bis (trimethylsilyl) amino salt MN (SiMe3) 2 to synthesize diaryl alkyne by a one-pot method. The raw materials and chemical reagents used in the method are easy to obtain, the reaction conditions are mild, the operation is simple, the substrate universality is good, the product yield is high, and the method is a simple and efficient diaryl alkyne synthesis method.
Synthesis of N-Heterocyclic Carbine Silver(I) and Palladium(II) Complexes with Acylated Piperazine Linker and Catalytic Activity in Three Types of C—C Coupling Reactions
Liu, Qingxiang,Zhang, Xiantao,Zhao, Zhixiang,Li, Xinying,Zhang, Wei
supporting information, p. 605 - 613 (2021/02/01)
Two bis-imidazolium salts LH2·Cl2 and LH2·(PF6)2 with acylated piperazine linker and two N-heterocyclic carbene (NHC) silver(I) and palladium(II) complexes [L2Ag2](PF6)2 (1) and [L2Pd2Cl4] (2) were prepared. The crystal structures of LH2·Cl2 and 1 were confirmed by X-ray analysis. In 1, one 26-membered macrometallocycle was generated through two silver(I) ions and two bidentate ligands L. The catalytic activity of 2 was investigated in Sonogashira, Heck-Mizoroki and Suzuki-Miyaura reactions. The results displayed that these C—C coupling reactions can be smoothly carried out under the catalysis of 2.
Si-Gly-CD-PdNPs as a hybrid heterogeneous catalyst for environmentally friendly continuous flow Sonogashira cross-coupling
Cravotto, Giancarlo,Ferlin, Francesco,Martina, Katia,Menzio, Janet,Sciosci, Daniele,Vaccaro, Luigi,Valentini, Federica
supporting information, p. 7210 - 7218 (2021/09/28)
We have reported a waste-minimized protocol for the Sonogashira cross-coupling exploiting the safe use of a CPME/water azeotropic mixture and the utilization of a heterogeneous hybrid palladium catalyst supported onto a silica/β-cyclodextrin matrix in con
A Waste-Minimized Approach to Cassar-Heck Reaction Based on POLITAG-Pd0 Heterogeneous Catalyst and Recoverable Acetonitrile Azeotrope
Valentini, Federica,Ferlin, Francesco,Tomarelli, Elena,Mahmoudi, Hamed,Bagherzadeh, Mojtaba,Calamante, Massimo,Vaccaro, Luigi
, p. 3359 - 3366 (2021/07/28)
Three different Pd0-based heterogeneous catalysts were developed and tested in the Cassar–Heck reaction (i. e., copper-free Sonogashira reaction) aiming at the definition of a waste minimized protocol. The cross-linked polymeric supports used in this investigation were designed to be adequate for different reaction media and were decorated with different pincer-type ionic ligands having the role of stabilizing the formation and dimension of palladium nanoparticles. Among the ionic tags tested, bis-imidazolium showed the best performances in terms of efficiency and durability of the metal catalytic system. Eventually, aqueous acetonitrile azeotrope was selected as the reaction medium as it allowed the best catalytic efficiency combined with easy recovery and reuse. Finally, the synergy between the selected catalyst and reaction medium allowed to obtain highly satisfactory isolated yields of a variety of substrates while using a low amount of metal catalyst. The high performance of the designed POLymeric Ionic TAG (POLITAG)-Pd0, along with its good selectivity achieved in a copper-free process, also led to a simplified purification procedure allowing the minimization of the waste generated as also proven by the very low E-factor values (1.4–5) associated.
Bimetallic Ni/Cu mesoporous silica nanoparticles as an efficient and reusable catalyst for the Sonogashira cross-coupling reactions
Nasresfahani, Zahra,Kassaee, Mohamad Z.
supporting information, (2021/02/12)
A bimetallic mesoporous system (Ni/Cu-MCM-41) has been developed and evaluated as an efficient catalyst for the Sonogashira cross-coupling reaction, under palladium-free conditions. In this new methodology, a wide range of aryl halides react with phenylacetylene to give the corresponding disubstituted alkynes in good yields. Moreover, the present catalytic system is desired because of its high efficiency, easy preparation, low cost, high activity, and good recyclability.
Electro-alkynylation: Intramolecular Rearrangement of Trialkynylorganoborates for Chemoselective C(sp2)-C(sp) Bond Formation
Didier, Dorian,Lemke, Yannick,Music, Arif,Nuber, Constantin M.,Spie?, Philipp
supporting information, p. 4179 - 4184 (2021/06/27)
An alternative and complementary transformation for the synthesis of aryl- and heteroaryl-substituted alkynes is presented that relies on a chemoselective electrocoupling process. Tetraorganoborate substrates were logically designed and simply accessed by transmetalations using readily or commercially available organotrifluoroborate salts.
Facile one-pot synthesis of diarylacetylenes from arylaldehydes: Via an addition-double elimination process
Chen, Jianyang,Zhang, Xuan,Wu, Jiajun,Wang, Rui,Lei, Chunlin,An, Yanan
, p. 4701 - 4705 (2021/06/11)
A practical one-pot protocol has been developed to synthesize diarylacetylenes from arylaldehydes by treatment with 1-(arylmethyl)benzotriazoles and LiN(SiMe3)2. The reaction proceeded through imine formation, Mannich-type addition and double elimination to deliver products in up to 99% yields with broad substrate scope. In addition, gram-scale synthesis of 1-bromo-4-(phenylethynyl)benzene has been demonstrated.
Copper(0) nanoparticle catalyzed Z-Selective Transfer Semihydrogenation of Internal Alkynes
Moran, Maria Jesus,Martina, Katia,Bieliunas, Vidmantas,Baricco, Francesca,Tagliapietra, Silvia,Berlier, Gloria,De Borggraeve, Wim M.,Cravotto, Giancarlo
supporting information, p. 2850 - 2860 (2021/05/06)
The use of copper(0) nanoparticles in the transfer semihydrogenation of alkynes has been investigated as a lead-free alternative to Lindlar catalysts. A stereo-selective methodology for the hydrogenation of internal alkynes to the corresponding (Z)-alkenes in high isolated yields (86% average) has been developed. This green and sustainable transfer hydrogenation protocol relies on non-noble copper nanoparticles for reduction of both electron-rich and electron-deficient, aliphatic-substituted and aromatic- substituted internal alkynes. Polyols, such as ethylene glycol and glycerol, have been proven to act as hydrogen sources, and excellent stereo- and chemoselectivity have been observed. Enabling technologies, such as microwave and ultrasound irradiation are shown to enhance heat and mass transfer, whether used alone or in combination, resulting in a decrease in reaction time from hours to minutes. (Figure presented.).
Ligand-Promoted Alkynylation of Aryl Ketones: A Practical Tool for Structural Diversity in Drugs and Natural Products
Xu, Hui,Ma, Biao,Fu, Zunyun,Li, Han-Yuan,Wang, Xing,Wang, Zhen-Yu,Li, Ling-Jun,Cheng, Tai-Jin,Zheng, Mingyue,Dai, Hui-Xiong
, p. 1758 - 1764 (2021/02/09)
Conversion of the numerous aryl ketones into aryl electrophiles via Ar-C(O) cleavage remains a challenging yet highly desirable transformation in Sonogashira-type coupling. Herein, we report a palladium-catalyzed ligand-promoted alkynylation of unstrained aryl ketones. The protocol allows the alkynylation to be carried out in a one-pot procedure with broad functional-group tolerance and substrate scope. The potential applications of this protocol in drug discovery and chemical biology are further demonstrated by late-stage diversification of a number of pharmaceuticals and natural products. More importantly, two different biologically important fragments derived from a pharmaceutical and natural product could be connected by the consecutive alkynylation of ketones. Distinct from aryl halides in conventional Sonogashira reactions, the protocol provides a practical tool for the 1,2-bifunctionalization of aryl ketone by merging ketone-directed ortho-C-H activation with ligand-promoted ipso-Ar-C(O) alkynylation.
