172507-33-4Relevant academic research and scientific papers
Electrosynthesis of 3-thienylzinc bromide from 3-bromothiophene via a nickel catalysis
Gosmini,Nedelec,Perichon
, p. 1941 - 1942 (1997)
3-Thienylzinc bromide is prepared under mild conditions by electroreduction of a DMF solution of 3-bromothiophene, zinc bromide, and a catalytic amount of nickel-bipyridine complex using a magnesium rod as sacrificial anode. The resulting organometallic is then coupled with aryl halides using a palladium catalysis.
Redox-Divergent Construction of (Dihydro)thiophenes with DMSO
Chen, Qing-An,He, Gu-Cheng,Hu, Yan-Cheng,Ji, Ding-Wei,Liu, Heng,Zhang, Xiang-Xin,Zhao, Chao-Yang
supporting information, p. 24284 - 24291 (2021/10/08)
Thiophene-based rings are one of the most widely used building blocks for the synthesis of sulfur-containing molecules. Inspired by the redox diversity of these features in nature, we demonstrate herein a redox-divergent construction of dihydrothiophenes, thiophenes, and bromothiophenes from the respective readily available allylic alcohols, dimethyl sulfoxide (DMSO), and HBr. The redox-divergent selectivity could be manipulated mainly by controlling the dosage of DMSO and HBr. Mechanistic studies suggest that DMSO simultaneously acts as an oxidant and a sulfur donor. The synthetic potentials of the products as platform molecules were also demonstrated by various derivatizations, including the preparation of bioactive and functional molecules.
Suzuki-Miyaura coupling catalyzed by a Ni(II) PNP pincer complex: Scope and mechanistic insights
Madera, Justin,Slattery, Megan,Arman, Hadi D.,Tonzetich, Zachary J.
, (2020/02/04)
The nickel(II) pincer complex, [NiCl(PhPNP)] (PhPNP = anion of 2,5-bis(diphenylphosphinomethyl)pyrrole), has been employed as a precatalyst for the Suzuki-Miyaura cross-coupling reaction of aryl halides and boronic acids. Both electron-rich and electron-deficient aromatic bromides were found to undergo coupling with boronic acids in modest yield at elevated temperature in the presence of K3PO4·H2O. Preliminary mechanistic studies of the reaction identified a novel species formulated as the boronate complex, [Ni(OB{OH}{2-tolyl})(PhPNP)], which most likely represents a catalyst deactivation pathway. The productive catalytic cycle was found to be most consistent with a Ni(I)/Ni(III) process where the boronic acid serves as both reductant and nucleophile in the presence of base.
Palladium-catalyzed decarbonylative Suzuki-Miyaura cross-coupling of amides by carbon-nitrogen bond activation
Zhou, Tongliang,Ji, Chong-Lei,Hong, Xin,Szostak, Michal
, p. 9865 - 9871 (2019/11/11)
Palladium-catalyzed Suzuki-Miyaura cross-coupling or aryl halides is widely employed in the synthesis of many important molecules in synthetic chemistry, including pharmaceuticals, polymers and functional materials. Herein, we disclose the first palladium-catalyzed decarbonylative Suzuki-Miyaura cross-coupling of amides for the synthesis of biaryls through the selective activation of the N-C(O) bond of amides. This new method relies on the precise sequence engineering of the catalytic cycle, wherein decarbonylation occurs prior to the transmetallation step. The reaction is compatible with a wide range of boronic acids and amides, providing valuable biaryls in high yields (>60 examples). DFT studies support a mechanism involving oxidative addition, decarbonylation and transmetallation and provide insight into high N-C(O) bond activation selectivity. Most crucially, the reaction establishes the use of palladium catalysis in the biaryl Suzuki-Miyaura cross-coupling of the amide bond and should enable the design of a wide variety of cross-coupling methods in which palladium rivals the traditional biaryl synthesis from aryl halides and pseudohalides.
Preparing method of aromatic nitrile or alkenyl nitrile compound
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Paragraph 0130-0132; 0199-0201; 0232-0233, (2019/10/01)
The invention discloses a preparing method of an aromatic nitrile or alkenyl nitrile compound. The preparing method comprises the following step that under protection of inert gas, an aryl or heteroaryl sulphonate compound shown in a formula II or an alkenyl sulphonate compound shown in a formula IV and a cyanation reagent are subjected to a cross-coupling reaction as is shown below in a solvent under the condition of the presence of a nickel complex, metal zinc and an additive to obtain the aromatic nitrile or alkenyl nitrile compound, wherein 4-dimethylamiopryidine (DMAP) is adopted as the additive, and zinc cyanide is adopted as the cyanation reagent. By means of the preparing method, cyanation of aryl sulphonate, heteroaryl sulphonate or alkenyl sulphonate can be simply and efficientlyachieved with a cheap catalysis system; moreover, the functional group compatibility and substrate universality are good, and a better application prospect and higher using value are provided for achieving industrial synthesis of the aromatic nitrile or alkenyl nitrile compound.
Nickel-Catalyzed Cyanation of Phenol Derivatives with Zn(CN)2 Involving C-O Bond Cleavage
Gan, Yi,Wang, Gaonan,Xie, Xin,Liu, Yuanhong
, p. 14036 - 14048 (2018/11/03)
An efficient nickel-catalyzed cyanation of aryl sulfonates, fluorosulfonates, and sulfamates with Zn(CN)2 was developed, which provides a facile access to the nitrile products in generally good to excellent yields. The reaction is accomplished by using NiII complex as the precatalyst and DMAP as the additive. The method also displays wide functional group compatibility; for example, keto, methoxy, N,N-dimethylamino, cyano, ester, and pyridyl groups are well-tolerated during the reaction process.
Suzuki-Miyaura Micellar Cross-Coupling in Water, at Room Temperature, and under Aerobic Atmosphere
Mattiello, Sara,Rooney, Myles,Sanzone, Alessandro,Brazzo, Paolo,Sassi, Mauro,Beverina, Luca
supporting information, p. 654 - 657 (2017/02/10)
Recently, oxygen-equilibrated water solutions of Kolliphor EL, a well-known surfactant, have been seen to form nanomicelles with oxygen-free cores. This has prompted the successful testing of the core environment as a green medium for palladium-catalyzed Suzuki-Miyaura cross couplings. The versatility of these conditions is endorsed by several examples, including the synthesis of relevant molecular semiconductors. The reaction medium can also be recycled, opening the way for an extremely easy and green chemistry compliant methodology.
Polymer nanoparticles with high photothermal conversion efficiency as robust photoacoustic and thermal theranostics
Guo, Liang,Liu, Weimin,Niu, Guangle,Zhang, Panpan,Zheng, Xiuli,Jia, Qingyan,Zhang, Hongyan,Ge, Jiechao,Wang, Pengfei
supporting information, p. 2832 - 2839 (2017/04/21)
Synthesis of photothermal agents with absorption in the near-infrared (NIR) region and featuring excellent photostability, high photothermal conversion efficiency, and good biocompatibility is necessary for the application of photothermal therapy (PTT). I
One-pot Suzuki coupling of aromatic amines via visible light photocatalyzed metal free borylation using t-BuONO at room temperature
Ahammed, Sabir,Nandi, Shiny,Kundu, Debasish,Ranu, Brindaban C.
, p. 1551 - 1554 (2018/03/29)
A convenient and efficient metal free borylation of aromatic amines has been achieved using tertiary butyl nitrite and B2Pin2 (bis(pinacolato)diborane) under irradiation with blue LED light at room temperature. This protocol has been successfully extended to subsequent Suzuki coupling in the same pot. Thus a series of functionalized aryl boronates and biaryls are obtained in high yields in a shorter reaction period starting from relatively cheap aryl amines in one-pot avoiding isolation of potentially unstable and hazardous intermediates.
Multimetallic catalysed cross-coupling of aryl bromides with aryl triflates
Ackerman, Laura K. G.,Lovell, Matthew M.,Weix, Daniel J.
, p. 454 - 457 (2015/09/08)
The advent of transition-metal catalysed strategies for forming new carbon-carbon bonds has revolutionized the field of organic chemistry, enabling the efficient synthesis of ligands, materials, and biologically active molecules. In cases where a single metal fails to promote a selective or efficient transformation, the synergistic cooperation of two distinct catalysts - multimetallic catalysis - can be used instead. Many important reactions rely on multimetallic catalysis, such as the Wacker oxidation of olefins and the Sonogashira coupling of alkynes with aryl halides, but this approach has largely been limited to the use of metals with distinct reactivities, with only one metal catalyst undergoing oxidative addition. Here, we demonstrate that cooperativity between two group 10 metal catalysts - (bipyridine)nickel and (1,3-bis(diphenylphosphino)propane)palladium - enables a general cross-Ullmann reaction (the cross-coupling of two different aryl electrophiles). Our method couples aryl bromides with aryl triflates directly, eliminating the use of arylmetal reagents and avoiding the challenge of differentiating between multiple carbon-hydrogen bonds that is required for direct arylation methods. Selectivity can be achieved without an excess of either substrate and originates from the orthogonal reactivity of the two catalysts and the relative stability of the two arylmetal intermediates. While (1,3-bis(diphenylphosphino)propane)palladium reacts preferentially with aryl triflates to afford a persistent intermediate, (bipyridine)nickel reacts preferentially with aryl bromides to form a transient, reactive intermediate. Although each catalyst forms less than 5 per cent cross-coupled product in isolation, together they are able to achieve a yield of up to 94 per cent. Our results reveal a new method for the synthesis of biaryls, heteroaryls, and dienes, as well as a general mechanism for the selective transfer of ligands between two metal catalysts. We anticipate that this reaction will simplify the synthesis of pharmaceuticals, many of which are currently made with pre-formed organometallic reagents, and lead to the discovery of new multimetallic reactions.
