共查询到20条相似文献,搜索用时 15 毫秒
1.
Dr. Gang Li Ki‐Young Yoon Xinjue Zhong Prof. Dr. Xiaoyang Zhu Prof. Dr. Guangbin Dong 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(27):9116-9120
Herein an efficient bottom‐up solution‐phase synthesis of N=9 armchair graphene nanoribbons (GNRs) is described. Catalyzed by Pd(PtBu3)2, Suzuki–Miyaura polymerization of a simple and readily available triaryl monomer provides a novel GNR precursor with a high molecular weight and excellent solubility. Upon cyclodehydrogenation, the resulting GNR exhibits semiconducting properties with an approximately 1.1 eV band gap (LUMO: ?3.52 eV; HOMO: ?4.66 eV) as characterized by UV/Vis‐NIR spectroscopy and cyclic voltammetry. 相似文献
2.
The Origin of Shape Sensitivity in Palladium‐Catalyzed Suzuki–Miyaura Cross Coupling Reactions 下载免费PDF全文
Dr. Gillian Collins Michael Schmidt Dr. Colm O'Dwyer Prof. Justin D. Holmes Dr. Gerard P. McGlacken 《Angewandte Chemie (International ed. in English)》2014,53(16):4142-4145
The shape sensitivity of Pd catalysts in Suzuki–Miyaura coupling reactions is studied using nanocrystals enclosed by well‐defined surface facets. The catalytic performance of Pd nanocrystals with cubic, cuboctahedral and octahedral morphologies are compared. Superior catalytic reactivity is observed for Pd NCs with {100} surface facets compared to {111} facets. The origin of the enhanced reactivity associated with a cubic morphology is related to the leaching susceptibility of the nanocrystals. Molecular oxygen plays a key role in facilitating the leaching of Pd atoms from the surface of the nanocrystals. The interaction of O2 with Pd is itself facet‐dependent, which in turn gives rise to more efficient leaching from {100} facets, compared to {111} facets under the reaction conditions. 相似文献
3.
Kentaro Kosaka Yoshihiro Ohta Tsutomu Yokozawa 《Macromolecular rapid communications》2015,36(4):373-377
Although water promotes Suzuki–Miyaura coupling reaction, it also induces side reactions such as deboronation and dehalogenation. Therefore, Suzuki–Miyaura polymerization of triolborate halothiophene monomer 1 with tBu3PPd(o‐tolyl)Br ( 2 ) in dry tetrahydrofuran (THF) is investigated. However, the resultant poly(3‐hexylthiophene) (P3HT) shows a broad molecular weight distribution and uncontrolled polymer ends. Model reactions of a number of boron reagents 3 with 2,5‐dibromothiophene ( 4 ) in the presence or absence of water indicate that intramolecular transfer of the catalyst is hardly affected by the boron moiety of 3 , whereas it is hindered in the absence of water. Indeed, polymerization of 1 with 2 in H2O/THF affords P3HT with a narrower molecular weight distribution and controlled tolyl/H ends, as compared to the reaction in dry THF.
4.
Mamoru Tobisu Dr. Naoto Chatani Prof. Dr. 《Angewandte Chemie (International ed. in English)》2009,48(20):3565-3568
Seeing the sites : The Suzuki–Miyaura reaction of substrates containing multiple coupling sites has been performed in a directed manner through the reactivity modulation of the boron moiety (see scheme). Several other strategies are also discussed.
5.
《化学:亚洲杂志》2017,12(14):1765-1772
The Ni‐catalyzed Suzuki–Miyaura coupling of N ‐tert‐butoxycarbonyl (N ‐Boc)‐protected amides provides a versatile strategy for the construction of C−C bonds. In this study, density functional theory (DFT) methods have been used to elucidate the mechanism of this reaction, with particular emphasis on the roles of N ‐Boc, K3PO4 and H2O. Our results corroborated those of previous reports, indicating that the overall catalytic cycle consists of three steps, including oxidative addition, transmetalation, and reductive elimination. Three of the possible transmetalation mechanisms were examined to interpret the effects of K3PO4 and H2O. According to the most feasible of these transmetalation mechanisms, K3PO4 (acting as a Lewis base) would initially interact with the Lewis acid PhBpin to give a K3PO4‐PhBpin complex, which would readily undergo a hydrogen transfer step with H2O. The H transfer in the transmetalation step was determined to be the rate‐determining step. Notably, the theoretical results showed good agreement with the experimental data. 相似文献
6.
Someswara Rao Kosuru Hsin‐Yu Lai Chien‐Yi Yang Gopal Chandru Senadi Yi‐Chun Lai Hsuan‐Ying Chen 《中国化学会会志》2019,66(1):110-113
The palladacycle complex [LsPdOAc]2 bearing 2‐phenyl benzothiazole was synthesized and characterized by NMR and X‐ray crystallography. [LsPdOAc]2 was used as a catalyst in the Suzuki–Miyaura cross coupling reaction of 4‐bromotoluene with phenylboronic acid, which resulted in a conversion of >90% with 5 mol% of the Pd complex within 10 min at 60°C. 相似文献
7.
8.
Axel Houdayer Raphaël Schneider Denis Billaud Jaafar Ghanbaja Jacques Lambert 《应用有机金属化学》2005,19(12):1239-1248
A novel route to prepare polyaniline (PANI)‐supported Pd(0) nanoparticles by a one‐pot chemical route is presented. Nanosized Pd(0) particles were first prepared by reduction of Pd(OAc)2 using t‐BuONa activated sodium hydride in refluxing THF. A ligand exchange with aniline on t‐BuONa‐stabilized Pd(0) particles yielded aniline‐stabilized particles. Pd(0)/PANI nanocomposites were finally obtained by polymerizing aniline‐stabilized Pd(0) particles using ammonium persulfate. Nanocomposites were characterized by transmission electron microscopy, X‐ray diffraction and X‐ray photoelectron spectroscopy. Results show that this one‐pot experimental route is successful in producing hybrid materials constituted of Pd(0) nanoparticles stabilized by PANI due to the strong binding of PANI amine groups to Pd(0) particles. TEM images of the nanohybrids show that metal particles with diameters of ca. 4.9 nm are homogeneously dispersed in PANI. The preliminary results indicate that the Pd(0) particles supported on PANI behave as efficient heterogeneous catalysts in the Heck and Suzuki–Miyaura reactions of aryl iodides. Copyright © 2005 John Wiley & Sons, Ltd. 相似文献
9.
Synthesis of Thiophene‐Based π‐Conjugated Oligomers via Ligand‐Enabled Pd‐Catalyzed Suzuki–Miyaura Coupling of Haloterthienyls 下载免费PDF全文
Jie Guo Yong Wu Prof. Dr. Fuk Yee Kwong Dr. Heng Zhang Prof. Dr. Aiwen Lei 《化学:亚洲杂志》2018,13(13):1660-1663
A ligand‐enabled Pd‐catalyzed Suzuki–Miyaura coupling of haloterthienyls for the synthesis of various thiophene‐based π‐conjugated oligomers including quinquethiophenes is demonstrated. An indolyl phosphine ligand plays an important role in this transformation. Thiopheneboronic acids were well applied, which might open up a window for the application of thiopheneboronic acids in the synthesis of thiophene‐based π‐conjugated oligomers in materials chemistry. 相似文献
10.
As one of the most powerful and versatile methods for the construction of carbon–carbon bonds, the Suzuki–Miyaura cross‐coupling reaction has attracted great attention over the past three decades. In recent years, a huge amount of interest has been focused on the development of ligand‐free Suzuki–Miyaura reaction systems, which have the advantages of low cost, mild reaction conditions, and easy operation. So far, a number of ligand‐free Suzuki–Miyaura reaction systems have been developed by using simple palladium salts, nanopalladium, or supported palladium catalysts. In this account, we will review our recent research on the oxygen‐promoted ligand‐free Suzuki–Miyaura reaction. Interestingly, the oxygen‐promoting effect has been observed in different reaction media, including polyethylene glycol, organic/water mixed solvents and pure water. The oxygen‐promoted reaction systems demonstrate high efficiency for the construction of biaryls.
11.
Wenjun Tang Dr. Andrew G. Capacci Xudong Wei Dr. Wenjie Li Dr. Andre White Dr. Nitinchandra D. Patel Jolaine Savoie Joe J. Gao Sonia Rodriguez Dr. Bo Qu Dr. Nizar Haddad Dr. Bruce Z. Lu Dr. Dhileepkumar Krishnamurthy Dr. Nathan K. Yee Dr. Chris H. Senanayake Dr. 《Angewandte Chemie (International ed. in English)》2010,49(34):5879-5883
12.
Josef Jansa Tomáš Řezníček Libor Dostál Zdena Růžičková Filip Bureš Roman Jambor 《应用有机金属化学》2016,30(12):1036-1042
We report a simple and efficient procedure for Suzuki–Miyaura reactions in aqueous media catalysed by amidophosphine‐stabilized palladium complexes trans‐{L3PPh2}2PdCl2 ( 3 ), trans‐{L3PPhtBu}2PdCl2 ( 4 ), [Pd(η3‐C3H5)(L3PPh2)Cl] ( 5 ) and {Pd[2‐(Me2NCH2)C6H4](L3PPh2)Cl} ( 6 ). The acidity of the NH proton in complexes 3 , 4 , 5 , 6 plays an important role in their catalytic activity. In addition, the palladium complexes cis‐{L1PPh2}PdCl2 ( 1 ) and trans‐{L2PPh2}2PdCl2 ( 2 ) stabilized by phosphines containing Y,C,Y‐chelating ligands L1,2 have also been found to be useful catalysts for Suzuki–Miyaura reactions in aqueous media. The method can be effectively applied to both activated and deactivated aryl bromides yielding high or moderate conversions. The catalytic activity of couplings performed in pure water increases when utilizing a Pd complex with more acidic NH protons. A decrease of palladium concentration from 1.0 to 0.5 mol% does not lead to a substantial loss of conversion. In addition, Pd complex 1 can be efficiently recovered using two‐phase system extraction. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
13.
An easily prepared tetraphosphine N,N,N′,N′‐tetra(diphenylphosphinomethyl)‐1,2‐ethylenediamine (1) combined with PdCl2 affords an efficient catalytic system for Suzuki cross‐coupling of aryl and heteroaryl bromides. A high turnover number of 750 000 is obtained with the catalyst loading as low as 1 ppm. This catalyst system exhibits good stability and longevity. In this study, a broad scope of substrates is investigated and satisfactory yields are obtained. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
14.
Investigation of Suzuki–Miyaura catalyst‐transfer polycondensation of AB‐type fluorene monomer using coordination‐saturated aryl Pd(II) halide complexes as initiators 下载免费PDF全文
Zilong Zhang Pan Hu Xiao Li Hongmei Zhan Yanxiang Cheng 《Journal of polymer science. Part A, Polymer chemistry》2015,53(12):1457-1463
Novel triarylamine‐based coordination‐saturated aryl Pd(II) halide complexes ligated by PEt3, PCy3, and P(o‐tol)3 were successfully synthesized by direct oxidative addition of aryl halide to the corresponding Pd(0) precursors. Suzuki–Miyaura coupling polymerization of 2‐(7‐halide‐9,9‐dioctylfluoren‐2‐yl)?1,3,2‐dioxaborinane with these Pd(II) complexes as initiators was investigated for the synthesis of poly(fluorene)s with triarylamine end group. Pd(II) complexes with PCy3 or P(o‐tol)3 exhibited catalytic activity and realized the catalyst‐transfer polycondensation at 75 °C and room temperature, respectively, while the polymerization using Pd(II) catalyst ligated by PEt3 did not proceed, which indicated that the bulky phosphine ligands could facilitate the reductive elimination and further promote the polymerization. In addition, the dimeric Pd(II) complex with P(o‐tol)3 can convert into monomeric Pd(II) intermediate with an open coordination site, which had a higher activity. The end groups of the afforded polyfluorene were analyzed by matrix‐assisted laser desorption ionization time‐of‐flight (MALDI‐TOF) mass spectrometry, in which the Ar/H end groups are indicative of the catalyst‐transfer polymerization. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1457–1463 相似文献
15.
Ying‐Tang Huang Xiao Tang Yi Yang Dong‐Sheng Shen Cheng Tan Feng‐Shou Liu 《应用有机金属化学》2012,26(12):701-706
A series of pyridylbenzamidine ligands were applied in palladium‐catalyzed Suzuki–Miyaura reactions and the effect of ligand on catalytic properties was evaluated. Under the optimization conditions, the bulky and electron‐donating nitrogen donor ligands were successfully used to catalyze the reaction of a variety of aryl bromides and aryl chlorides with arylboronic acid, giving the desired products in moderate to high yields. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
16.
An easily prepared tetraphosphine N,N,N′,N′‐tetra(diphenylphosphinomethyl)‐1,2‐ethylenediamine (L1) associated with [Pd(η3‐C3H5)Cl]2 affords an efficient catalyst for Suzuki–Miyaura coupling of 3‐pyridineboronic acid with heteroaryl bromides. Reaction could be performed with as little as 0.02 mol% catalyst and a high turnover number of 2500 is obtained. A wide range of substrates is investigated with satisfactory yields, and good compatibility with aminogroup‐substituted pyridines and unprotected indole is exhibited. This protocol can also be applied successfully to the reaction of heteroaryl bromides with 3‐thiopheneboronic acid. This Pd‐tetraphosphine catalyst efficiently restrains the poisoning effect from heteroaryls, and shows good stability and longevity. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
17.
Dr. Christian Amatore Dr. Gaëtan Le Duc Dr. Anny Jutand 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(31):10082-10093
In Suzuki–Miyaura reactions, anionic bases F? and OH? (used as is or generated from CO32? in water) play multiple antagonistic roles. Two are positive: 1) formation of trans‐[Pd(Ar)F(L)2] or trans‐[Pd(Ar)‐ (L)2(OH)] (L=PPh3) that react with Ar′B(OH)2 in the rate‐determining step (rds) transmetallation and 2) catalysis of the reductive elimination from intermediate trans‐[Pd(Ar)(Ar′)(L)2]. Two roles are negative: 1) formation of unreactive arylborates (or fluoroborates) and 2) complexation of the OH group of [Pd(Ar)(L)2(OH)] by the countercation of the base (Na+, Cs+, K+). 相似文献
18.
《应用有机金属化学》2017,31(11)
A semi‐synthetic method has been developed for the synthesis of aminoarylbenzosuberenes (AABs) from naturally occurring himachalenes, an isomeric mixture of sesquiterpenes present in Cedrus deodara oil. Polymer‐stabilized Pd(0) nanoparticle‐catalysed Suzuki–Miyaura cross‐coupling reaction of aminovinyl bromide‐substituted benzosuberenes has been adopted for AAB synthesis. The catalyst performed well with different amine substituents, and was recycled up to five times. The synthesis of such arylated benzosuberene class of compounds from natural precursors following semi‐synthetic approaches could provide an attractive alternative method with reduced number of steps. 相似文献
19.
Masataka Nojima Takeru Kamigawara Yoshihiro Ohta Tsutomu Yokozawa 《Journal of polymer science. Part A, Polymer chemistry》2019,57(3):297-304
We report Suzuki–Miyaura coupling polymerization of tetraalkoxy‐substituted 4‐bromostilbene‐4′‐boronic acid 1 with several t‐Bu3P‐ligated Pd initiators; this is the first example of catalyst‐transfer condensation polymerization (CTCP) of a monomer containing a carbon–carbon double bond. When o‐tolylPd(tBu3P)Br was used as the initiator, the o‐tolyl group was not introduced at the polymer end, but polymer with boronic acid at one end and bromine at the other was obtained. However, when we employed stilbenePd(tBu3P)I generated in situ from iodostilbene and Pd(tBu3P)G2 precatalyst, or isolated ArPd(tBu3P)X (Ar, X = Ph, I; o‐tolyl, I; and Ph, Br), the aryl group was introduced at the polymer end, indicating that CTCP of 1 proceeded. Therefore, the iodide and aryl group of the Pd initiator complex is crucial for CTCP of 1 . However, the molecular weight distribution of the obtained polymer was broad, possibly because coordination of the carbon–carbon double bond of 1 to ArPd(tBu3P)I resulted in slow initiation. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 297–304 相似文献