- Ligand-free, atom-efficient Suzuki-Miyaura type cross-coupling reactions at room temperature
-
The atom-efficient cross-coupling reaction of sodium tetraarylborates with aryl iodides and bromides was reported. The reaction can be performed directly using a catalytic system composed of palladium chloride, sodium carbonate and methanol (PdCl2/Na2CO3/MeOH) under heat-free conditions at room temperature in an open air conditions. The reactions carried out in an atom-efficient way as 4 equiv of aryl halides coupled effectively with 1 equiv of sodium tetraarylborates to furnish 4 equiv of the corresponding functionalized biaryls in good to excellent yields.
- Zhou, Wen-Jun,Wang, Ke-Hu,Wang, Jin-Xian,Gao, Zhi-Rong
-
-
Read Online
- Nickel-metalated porous organic polymer for Suzuki-Miyaura cross-coupling reaction
-
A new Ni(ii)-α-diimine-based porous organic polymer, namely Ni(ii)-α-diimine-POP, was constructed in high yield via the Sonogashira coupling reaction between the metallo-building block of Ni(ii)-α-diimine and 1,3,5-triethynylbenzene. Besides the high thermal and chemical stability, the obtained Ni(ii)-α-diimine-POP can be a highly active reusable heterogeneous catalyst to promote the Suzuki-Miyaura coupling reaction. The obtained results indicate that the Ni(ii)-α-diimine-POP herein is a promising sustainable alternative to the Pd-based catalysts for catalysing the C-C formation in a heterogeneous way.
- Dong, Ying,Jv, Jing-Jing,Li, Yue,Li, Wen-Han,Chen, Yun-Qi,Sun, Qian,Ma, Jian-Ping,Dong, Yu-Bin
-
-
Read Online
- Palladium-catalyzed cross-coupling reaction by means of organogermanium trichlorides
-
Easily accessible arylgermanium trichlorides were found to undergo palladium-catalyzed cross-coupling reactions with aryl bromides and iodides in good yields. The reaction is performed in an aqueous medium with sodium hydroxide as an activator. Some base-
- Enokido, Tatsuki,Fugami, Keigo,Endo, Mayuko,Kameyama, Masayuki,Kosugi, Masanori
-
-
Read Online
- Reusable, polystyrene-resin-supported, palladium-catalyzed, atom-efficient cross-coupling reaction of aryl halides with triarylbismuths
-
A rapid, atom-efficient, cross-coupling reaction of triarylbis- muths with aryl bromides or aryl iodides was reported, and the reaction involves the use of a catalytic amount of polystyrene-supported palladium in the presence of KF as base in DMSO at 105 0C in an open atmosphere. All three aryl groups of the triarylbismuths participated in the reaction and produced polyfunctional biaryls in excellent yields. The polymeric catalyst can be easily separated from the reaction mixture and reused more than 10 times without showing any obvious decrease in activity.
- Zhou, Wen-Jun,Wang, Ke-Hu,Wang, Jin-Xian,Huang, Dan-Feng
-
-
Read Online
- Cyclodextrin-supported palladium complex: A highly active and recoverable catalyst for Suzuki–Miyaura cross-coupling reaction in aqueous medium
-
A water-soluble, cyclodextrin-supported palladium complex (DACH-Pd-β-CD) catalytic system was designed and synthesized, which can efficiently catalyze Suzuki–Miyaura cross-coupling reactions between aryl halides and arylboronic acid in water under mild conditions. The catalyst was successfully characterized using the methods of transmission electron microscopy, energy-dispersive X-ray spectrometry, X-ray diffraction, thermogravimetric analysis, and Fourier transform infrared and NMR spectroscopies. Furthermore, the catalyst can be easily separated from the reaction mixture and still maintain high catalytic activity after ten cycles. No leaching of palladium into the reaction solution occurred. The advantages of green solvent (water), short reaction times (2–6?h), low catalyst loading (0.001?mol%), excellent yields (up to 99%) and reusability of the catalyst mean it will have potential applications in green chemical synthesis.
- Guo, Yafei,Li, Jiuling,Shi, Xiwei,Liu, Yang,Xie, Kai,Liu, Yuqi,Jiang, Yubo,Yang, Bo,Yang, Rui
-
-
Read Online
- Discovery of Biphenyl-Sulfonamides as Novel β- N-Acetyl- d -Hexosaminidase Inhibitors via Structure-Based Virtual Screening
-
Novel insecticidal targets are always in demand due to the development of resistance. OfHex1, a β-N-acetyl-d-hexosaminidase identified in Ostrinia furnacalis (Asian corn borer), is involved in insect chitin catabolism and has proven an ideal target for insecticide development. In this study, structure-based virtual screening, structure simplification, and biological evaluation are used to show that compounds with a biphenyl-sulfonamide skeleton have great potential as OfHex1 inhibitors. Specifically, compounds 10k, 10u, and 10v have Ki values of 4.30, 3.72, and 4.56 μM, respectively, and thus, they are more potent than some reported nonglycosyl-based inhibitors such as phlegmacin B1 (Ki = 26 μM), berberine (Ki = 12 μM), 2 (Ki = 11.2 μM), and 3 (Ki = 28.9 μM). Furthermore, inhibitory kinetic assessments reveal that the target compounds are competitive inhibitors with respect substrate, and based on toxicity predictions, most of them have potent drug properties. The obtained results indicate that the biphenyl-sulfonamide skeleton characterized by simple chemical structure, synthetic tractability, potent activity, and low toxicity has potential for further development in pest management targeting OfHex1.
- Chen, Tao,Li, Wen-Qin,Liu, Zheng,Jiang, Wen,Liu, Tian,Yang, Qing,Zhu, Xiao-Lei,Yang, Guang-Fu
-
p. 12039 - 12047
(2021/10/20)
-
- Ferrocenyl palladacycles derived from unsymmetrical pincer-type ligands: Evidence of Pd(0) nanoparticle generation during the Suzuki-Miyaura reaction and applications in the direct arylation of thiazoles and isoxazoles
-
A new family of ferrocenyl-palladacycle complexes Pd(L1)Cl (Pd1) and Pd(L2)Cl (Pd2) were synthesized and characterized by UV-visible, IR, ESI-MS, and NMR spectral studies. The molecular structures of Pd1 and Pd2 were determined by X-ray crystallographic studies. Palladacycle catalyzed Suzuki-Miyaura cross-coupling reactions were investigated utilizing the derivatives of phenylboronic acids and substituted chlorobenzenes. Mechanistic investigation authenticated the generation of Pd(0) nanoparticles during the catalytic cycle and the nanoparticles were characterized by XPS, SEM and TEM analysis. Direct C-H arylation of thiazole and isoxazole derivatives employing these ferrocenyl-palladacycle complexes was examined. The reaction model for the arylation reaction implicating the in situ generation of Pd(0) nanoparticles was proposed.
- Maji, Ankur,Singh, Anshu,Mohanty, Aurobinda,Maji, Pradip K.,Ghosh, Kaushik
-
supporting information
p. 17083 - 17096
(2019/11/26)
-
- Alpha-diimine nickel metal organic ligand, porous organic polymer and application of porous organic polymer
-
The disclosure provides an alpha-diimine nickel metal organic ligand, a porous organic polymer and application of the porous organic polymer. The porous organic polymer has a chemical structural formula as shown in the description. The porous organic polymer can be applied to preparation of a catalyst for catalyzing a Suzuki coupling reaction, and the catalyst has high catalytic activity, low cost, low usage amount and repeated use.
- -
-
Paragraph 0092-0093; 0106-0111
(2019/10/01)
-
- A palladium-carbon-connected organometallic framework and its catalytic application
-
Herein, we report an organometallic framework (OMF) generated from a divergent tridentate arylisocyanide ligand and PdI2 under solvothermal conditions. The obtained Pd-C bond-connected two-dimensional Pd-OMF was crystalline and porous. Moreover, it could be a highly active catalyst to promote the Suzuki-Miyaura cross-coupling reaction in a heterogeneous manner.
- Dong, Ying,Jv, Jing-Jing,Wu, Xiao-Wei,Kan, Jing-Lan,Lin, Ting,Dong, Yu-Bin
-
supporting information
p. 14414 - 14417
(2019/12/09)
-
- DIARYLUREAS AS CB1 ALLOSTERIC MODULATORS
-
The present invention provides novel diarylurea derivatives (compounds of formula (I)) and their uses. The compounds of the present invention are demonstrated to be allosteric modulators of the CB1 receptor, and therefore useful for the treatment of diseases and conditions mediated by CB1.
- -
-
Paragraph 69; 72; 86
(2018/12/02)
-
- An Active Palladium Colloidal Catalyst for the Selective Oxidative Heterocoupling of (Hetero)Aryl Boronic Acids
-
A highly selective oxidative heterocoupling protocol for (hetero)aryl boronic acids with an active palladium colloidal catalyst was developed. The judicious choice of electronically different aryl boronic acids made possible such couplings under mild conditions, with air as oxidant, while embracing a wide substrate scope. This successful approach further allowed the development of a unique one-pot sequential oxidative heterocoupling/Suzuki–Miyaura cross-coupling tandem process for accessing substituted terphenyls.
- Sable, Vaibhav,Maindan, Karan,Bhilare, Shatrughn,Chrysochos, Nicolas,Schulzke, Carola,Kapdi, Anant R.
-
supporting information
p. 2489 - 2498
(2018/09/10)
-
- Recyclable Pd/CuFe2O4 nanowires: A highly active catalyst for C-C couplings and synthesis of benzofuran derivatives
-
Pd/CuFe2O4 nanowire-catalyzed cross coupling transformations are described. Notably, these reactions showed excellent functional group tolerance. Further, the protocol is applied to a one-pot synthesis of benzofurans via a Sonogashira coupling and intramolecular etherification sequence. The catalyst was reused and found to maintain its activity and stability.
- Lakshminarayana, Bhairi,Chakraborty, Jhonti,Satyanarayana,Subrahmanyam, Ch.
-
p. 21030 - 21039
(2018/06/13)
-
- Novel Diarylurea Based Allosteric Modulators of the Cannabinoid CB1 Receptor: Evaluation of Importance of 6-Pyrrolidinylpyridinyl Substitution
-
Allosteric modulators of the cannabinoid CB1 receptor have recently been reported as an alternative approach to modulate the CB1 receptor for therapeutic benefits. In this study, we report the design and synthesis of a series of diarylureas derived from PSNCBAM-1 (2). Similar to 2, these diarylureas dose-dependently inhibited CP55,940-induced intracellular calcium mobilization and [35S]GTP-γ-S binding while enhancing [3H]CP55,940 binding to the CB1 receptor. Structure-activity relationship studies revealed that the pyridinyl ring of 2 could be replaced by other aromatic rings and the pyrrolidinyl ring is not required for CB1 allosteric modulation. 34 (RTICBM-74) had similar potencies as 2 in all in vitro assays but showed significantly improved metabolic stability to rat liver microsomes. More importantly, 34 was more effective than 2 in attenuating the reinstatement of extinguished cocaine-seeking behavior in rats, demonstrating the potential of this diarylurea series as promising candidates for the development of relapse treatment of cocaine addiction.
- Nguyen, Thuy,German, Nadezhda,Decker, Ann M.,Langston, Tiffany L.,Gamage, Thomas F.,Farquhar, Charlotte E.,Li, Jun-Xu,Wiley, Jenny L.,Thomas, Brian F.,Zhang, Yanan
-
p. 7410 - 7424
(2017/09/22)
-
- Catalytic Decarboxylative Cross-Coupling of Aryl Chlorides and Benzoates without Activating ortho Substituents
-
The restriction of decarboxylative cross-coupling reactions to ortho-substituted or heterocyclic carboxylate substrates was overcome by holistic optimization of a bimetallic Cu/Pd catalyst system. The combination of a CuI/Me4phen decarboxylation catalyst and a [(MeCN)4Pd](OTf)2/XPhos cross-coupling catalyst enables the synthesis of biaryls from inexpensive aryl chlorides and potassium benzoates regardless of their substitution pattern. Lifting the restriction: A combination of a CuI/Me4phen decarboxylation catalyst and a [(MeCN)4Pd](OTf)2/XPhos cross-coupling catalyst enables the synthesis of biaryls from inexpensive aryl chlorides and potassium benzoates regardless of their substitution pattern (see scheme; FG=functional group). This approach lifts the restriction of decarboxylative cross-coupling reactions to ortho-substituted or heterocyclic carboxylate substrates.
- Tang, Jie,Biafora, Agostino,Goossen, Lukas J.
-
supporting information
p. 13130 - 13133
(2015/11/02)
-
- Biaryl and aryl ketone synthesis via Pd-catalyzed decarboxylase coupling of carboxylate salts with aryl triflates
-
A bimetallic catalyst system has been developed that for the first time allows the decarboxylative crosscoupling of aryl and acyl carboxylates with aryl triflates. In contrast to aryl halides, these electrophiles give rise to non-coordinating anions as byproducts, which do not interfere with the decarboxylation step that leads to the generation of the carbon nucleophilic crosscoupling partner. As a result, the scope of carboxylate substrates usable in this transformation was extended from ortho-substituted or otherwise activated derivatives to a broad range of ortho-, meta-, and para-substituted aromatic carboxylates. Two alternative protocols have been optimized, one involving heating the substrates in the presence of CuI/1,10- phenanthroline (10-15 mol %) and PdI2/phosphine (23 mol%) in NMP for 1-24 h, the other involving CuI/l,10-phenanthroline (615mol%) and PdBr2/Tol-BINAP (2 mol % ) in NMP using microwave heating for 5-10 min. While most products are accessible using standard heating, the use of microwave irradiation was found to be beneficial especially for the conversion of non-activated carboxylates with functionalized aryl triflates. The synthetic utility of the transformation is demonstrated with 48 examples showing the scope and limitations of both protocols. In mechanistic studies, the special role of microwave irradiation is elucidated, and further perspectives of decarboxylase crosscouplings are discussed.
- Goossen, Lukas J.,Linder, Christophe,Rodriguez, Nuria,Lange, Paul P.
-
supporting information; experimental part
p. 9336 - 9349
(2010/04/03)
-
- Microwave-assisted Suzuki coupling reactions with an encapsulated palladium catalyst for batch and continuous-flow transformations
-
This article describes the design, optimisation and development of a Suzuki cross-coupling protocol mediated by an efficient palladium-en-capsulated catalyst (Pd EnCat) under microwave irradiation. The methodology has been used in both batch mode for classical library preparation and in continuous-flow applications furnishing multigram quantities of material. Described is a method that uses direct focused microwave heating whilst applying an external cooling source. This enables a lower than normal bulk temperature to be maintained throughout the reaction period leading to significant improvements in the overall yield and purity of the reaction products. Additional aspects of this novel heating protocol are discussed in relation to the prolonged lifetime and enhanced reactivity of the immobilised catalyst system.
- Baxendale, Ian R.,Griffiths-Jones, Charlotte M.,Ley, Steven V.,Tranmer, Geoffrey K.
-
p. 4407 - 4416
(2008/02/07)
-
- F-NMR-spectroscopy for the identification of photo products generated from aromatic iodo compounds - IV
-
The investigation demonstrates the analytical power of F-NMR spectroscopy for the identification of isomeric substituted fluorobiphenyls.The biphenyls are formed by u.v. irradiation of iodobenzenes in aromatic solvents.A special procedure for the identification is outlined and tendencies of the results-chemical shifts and relative rates for the production of isomers-are discussed in consideration of electronic and steric substituent effects.
- Kelm, J.,Strauss, K.
-
p. 689 - 692
(2007/10/02)
-