19617-68-6Relevant academic research and scientific papers
New Nickel-Based Catalytic System with Pincer Pyrrole-Functionalized N-Heterocyclic Carbene as Ligand for Suzuki-Miyaura Cross-Coupling Reactions
Guo, Zhifo,Lei, Xiangyang
supporting information, (2021/09/11)
A new catalytic system with Ni(NO3)2·6H2O as the catalyst and a pincer pyrrole-functionalized N-heterocyclic carbene as the ligand was employed in the Suzuki-Miyaura cross-coupling reactions of aryl iodides with arylboronic acids. With 5 mol% catalyst, the catalytic reactions proceeded at 160 °C, giving coupling products in isolated yields of up to 94% in short reaction times (1-4 h). The system worked efficiently with aryl iodides bearing electron-donating or electron-withdrawing groups and arylboronic acids with electron-donating groups. Steric effects were observed for both aryl iodides and arylboronic acids. It is proposed that the reactions underwent a Ni(I)/Ni(III) catalytic cycle.
Decarbonylative Suzuki-Miyaura Cross-Coupling of Aroyl Chlorides
Zhou, Tongliang,Xie, Pei-Pei,Ji, Chong-Lei,Hong, Xin,Szostak, Michal
supporting information, p. 6434 - 6440 (2020/09/02)
Herein, we report a catalyst system for Pd-catalyzed decarbonylative Suzuki-Miyaura cross-coupling of aroyl chlorides with boronic acids to furnish biaryls. This strategy is suitable for a broad range of common aroyl chlorides and boronic acids. The synthetic utility is highlighted in the direct late-stage functionalization of pharmaceuticals and natural products capitalizing on the presence of carboxylic acid moiety. Extensive mechanistic and DFT studies provide key insight into the reaction mechanism and high decarbonylative cross-coupling selectivity.
Palladium-catalysed room-temperature Suzuki–Miyaura coupling in water extract of pomegranate ash, a bio-derived sustainable and renewable medium
Appa, Rama Moorhy,Prasad, S. Siva,Lakshmidevi, Jangam,Naidu, Bandameeda Ramesh,Narasimhulu, Manchala,Venkateswarlu, Katta
, (2019/08/12)
An agro waste-derived, ‘water extract of pomegranate ash’ (WEPA), has been utilized for the first time as a renewable medium for Pd(OAc)2-catalysed Suzuki–Miyaura cross-coupling at room temperature. This method offers a simple and sustainable synthesis of biaryls from aryl halides and arylboronic acids under ligand- and external base-free aerobic and ambient conditions. This method has been found effective for both activated and unactivated aryl halides in the production of biaryls with moderate to nearly quantitative yields. The protocol shows high chemoselectivity over identical/similar reactive sites in aryl halides (i.e. selectivity over identical halogens or different halogens of aryl halides). This method exhibits high regioselectivity, i.e. the selective reactivity of a halogen over other identical halogens at different positions on the aromatic nucleus. Therefore, we disclose here a clean, benign, substantial chemo- and regioselective and highly economic alternative method for the palladium-assisted synthesis of biaryls using an agro waste-derived medium.
Cobalt-Catalyzed Cross-Coupling Reactions of Arylboronic Esters and Aryl Halides
Duong, Hung A.,Wu, Wenqin,Teo, Yu-Yuan
supporting information, p. 4363 - 4366 (2017/12/05)
An efficient cobalt catalyst system for the Suzuki-Miyaura cross-coupling reaction of arylboronic esters and aryl halides has been identified. In the presence of cobalt(II)/terpyridine catalyst and potassium methoxide, a diverse array of (hetero)biaryls have been prepared in moderate to excellent yields.
Mechanism insight and scope of PEPPSI-catalyzed cross-coupling reaction between triarylbismuth and arylbromide
Cassirame, Bénédicte,Condon, Sylvie,Pichon, Christophe
, p. 94 - 102 (2016/10/04)
In this paper we report the first cross-coupling reaction of Ar3Bi with Ar'X mediated by Pd-NHC complexes by keeping the ability of Ar3Bi to transfer the three aryl moieties. Investigations were carried out in order to minimize the quantity of the side product Ar-Ar coming from the conversion of Ar3Bi. The results showed that PEPPSI IPr was a good catalyst precursor. Efforts were focussed on the rule of each additive such as PPh3 and the base. It was notably found that the presence of PPh3 (ratio PEPPSI IPr/PPh3: 1/1) was essential to keep the process efficient. Therefore NHC-Pd-PPh3 has been assumed as being the catalytic species. Under the optimized reaction conditions the concomitant formation of the undesired biaryl side product was restricted to its inherent formation consecutive to the reduction of the catalyst precursor to Pd(0). In a last study, the scope and the limitation of the new catalytic methodology were examined and a large range of unsymmetrical biaryl compounds Ar-Ar’ bearing various substituents from strongly electron-donating to electron-withdrawing ones have been prepared and fully characterized.
An Indefinitely Air-Stable σ-NiII Precatalyst for Quantitative Cross-Coupling of Unreactive Aryl Halides and Mesylates with Aryl Neopentylglycolboronates
Malineni, Jagadeesh,Jezorek, Ryan L.,Zhang, Na,Percec, Virgil
supporting information, p. 2795 - 2807 (2016/08/31)
Three classes of Ni precatalysts based on π-NiII, π-Ni0 and σ-NiII complexes have been elaborated and employed in different laboratories for the functionalization and cross-coupling of otherwise inert aryl C-O, C-Cl, and C-F electrophiles. Various Ni precatalysts, ligands, boron sources, and reaction conditions that were developed in various research groups, necessitated the selection of the most suitable conditions for desired cross-coupling partners. Here a universal, bench-stable, easily prepared NiIICl(1-naphthyl)(PCy3)2/PCy3 σ-complex, for efficient and quantitative cross-coupling of aryl chlorides, bromides, iodides, mesylates, and fluorides with aryl neopentylglycolboronates is reported. This precatalyst will most probably help to advance the applications of Ni catalysis in organic, supramolecular, and macromolecular synthesis and will provide an easier access to the selection of reaction conditions for various transformations.
Very efficient and broad-in-scope palladium-catalyzed Hiyama cross-coupling. the role of water and copper(I) salts
Traficante, Carla I.,Mata, Ernesto G.,Delpiccolo, Carina M. L.
, p. 26796 - 26800 (2015/03/30)
A very high-yielding Pd-catalyzed cross-coupling between aryl halides and aryl(trialkoxy)silanes is achieved in the presence of Cu(i) and a measured amount of water. This novel methodology is useful for the generation of a wide range of biaryls, particularly non-para substituted derivatives, which are usually less reported.
Palladium-catalyzed cross-coupling reactions of arylsiloxanes with aryl halides: Application to solid-supported organic synthesis
Traficante, Carla I.,Delpiccolo, Carina M. L.,Mata, Ernesto G.
supporting information, p. 211 - 214 (2014/06/09)
The solid-phase version of the Pd-catalyzed Hiyama reaction between a variety of aryltriethoxysilanes and immobilized aryl halides was developed. Smooth cross-coupling was achieved to afford the corresponding biaryl products in moderate to excellent yields. The described protocol would be particularly useful for the construction of 4′-substituted 1,1′-biphenyl derivatives.
Arene-metal π-complexation as a traceless reactivity enhancer for C-H arylation
Ricci, Paolo,Kraemer, Katrina,Cambeiro, Xacobe C.,Larrosa, Igor
supporting information, p. 13258 - 13261 (2013/09/24)
Current approaches to facilitate C-H arylation of arenes involve the use of either strongly electron-withdrawing substituents or directing groups. Both approaches require structural modification of the arene, limiting their generality. We present a new approach where C-H arylation is made possible without altering the connectivity of the arene via π-complexation of a Cr(CO)3 unit, greatly enhancing the reactivity of the aromatic C-H bonds. We apply this approach to monofluorobenzenes, highly unreactive arenes, which upon complexation become nearly as reactive as pentafluorobenzene itself in their couplings with iodoarenes. DFT calculations indicate that C-H activation via a concerted metalation-deprotonation transition state is facilitated by the predisposition of C-H bonds in (Ar-H)Cr(CO)3 to bend out of the aromatic plane.
Iridium(iii) complexes with enhanced film amorphism as guests for efficient orange solution-processed single-layer PhOLEDs with low efficiency roll-off
Dai, Jun,Zhou, Kaifeng,Li, Ming,Sun, Huiqin,Chen, Yunqing,Su, Shijian,Pu, Xuemei,Huang, Yan,Lu, Zhiyun
, p. 10559 - 10571 (2013/07/26)
By introducing a phenyl substituent into the meta-site of the phenyl segment of the 2-phenylbenzothiazole ligand, two novel orange iridium(iii) complexes, namely, (3Phbt)2Ir(acac) and (3OMePhbt) 2Ir(acac), have been synthesized. Compared with their parent compound (bt)2Ir(acac), both of them possess much enhanced thermostability and film amorphism, making them suitable candidates as guests for high performance solution-processed phosphorescent organic light-emitting diodes (PhOLEDs). However, (4Phbt)2Ir(acac) bearing para-phenyl possesses worse processability relative to (bt)2Ir(acac) due to spontaneous crystallization stemming from the intense intermolecular interactions. Single-layer solution-processed PhOLEDs with (3Phbt)2Ir(acac) and (3OMePhbt)2Ir(acac) as guests show peak current efficiency of 17.2 cd A-1 and 15.2 cd A-1, and maximum brightness of 28 270 cd m-2 and 27 900 cd m-2, respectively. Both are greatly improved compared to the devices employing (bt)2Ir(acac) (10.2 cd A-1 and 14 350 cd m-2) and (4Phbt)2Ir(acac) (5.0 cd A-1 and 13 790 cd m-2) as phosphors. Moreover, quite low efficiency roll-off is acquired in these devices at high luminance. The much improved electroluminescence performances of these objective complexes could be mainly attributed to the presence of a rigid phenyl on the appropriate substitution site of the cyclometallate ligand, which leads to improved thermostability with compatible alleviated intermolecular interactions, and consequently enhanced film amorphism.
