- Desulfonative Suzuki–Miyaura Coupling of Sulfonyl Fluorides
-
Sulfonyl fluorides have emerged as powerful “click” electrophiles to access sulfonylated derivatives. Yet, they are relatively inert towards C?C bond forming transformations, notably under transition-metal catalysis. Here, we describe conditions under which aryl sulfonyl fluorides act as electrophiles for the Pd-catalyzed Suzuki–Miyaura cross-coupling. This desulfonative cross-coupling occurs selectively in the absence of base and, unusually, even in the presence of strong acids. Divergent one-step syntheses of two analogues of bioactive compounds showcase the expanded reactivity of sulfonyl fluorides to encompass both S?Nu and C?C bond formation. Mechanistic experiments and DFT calculations suggest oxidative addition occurs at the C?S bond followed by desulfonation to form a Pd-F intermediate that facilitates transmetalation.
- Bahadori, Maryam,Brykczyńska, Daria,Chatelain, Paul,Moran, Joseph,Muller, Cyprien,Rowley, Christopher N.,Sau, Abhijit
-
p. 25307 - 25312
(2021/10/25)
-
- Base-Activated Latent Heteroaromatic Sulfinates as Nucleophilic Coupling Partners in Palladium-Catalyzed Cross-Coupling Reactions
-
Heteroaromatic sulfinates are effective nucleophilic reagents in Pd0-catalyzed cross-coupling reactions with aryl halides. However, metal sulfinate salts can be challenging to purify, solubilize in reaction media, and are not tolerant to multi-step transformations. Here we introduce base-activated, latent sulfinate reagents: β-nitrile and β-ester sulfones. We show that under the cross-coupling conditions, these species generate the sulfinate salt in situ, which then undergo efficient palladium-catalyzed desulfinative cross-coupling with (hetero)aryl bromides to deliver a broad range of biaryls. These latent sulfinate reagents have proven to be stable through multi-step substrate elaboration, and amenable to scale-up.
- Blakemore, David C.,Cook, Xinlan A. F.,Moses, Ian B.,Pantaine, Lo?c R. E.,Sach, Neal W.,Shavnya, Andre,Willis, Michael C.
-
p. 22461 - 22468
(2021/09/09)
-
- Generation of Organozinc Reagents from Arylsulfonium Salts Using a Nickel Catalyst and Zinc Dust
-
Readily available aryldimethylsulfonium triflates react with zinc powder under nickel catalysis via the selective cleavage of the sp2-hybridized carbon-sulfur bond to produce salt-free arylzinc triflates under mild conditions. This zincation displays superb chemoselectivity and thus represents a protocol that is complementary or orthogonal to existing methods. The generated arylzinc reagents show both high reactivity and chemoselectivity in palladium-catalyzed and copper-mediated cross-coupling reactions.
- Yamada, Kodai,Yanagi, Tomoyuki,Yorimitsu, Hideki
-
p. 9712 - 9718
(2021/01/09)
-
- Merging C-H Vinylation with Switchable 6π-Electrocyclizations for Divergent Heterocycle Synthesis
-
Pyridinium-containing polyheterocycles exhibit distinctive biological properties and interesting electrochemical and optical properties and thus are widely used as drugs, functional materials, and photocatalysts. Here, we describe a unified two-step strategy by merging Rh-catalyzed C-H vinylation with two switchable electrocyclizations, including aza-6π-electrocyclization and all-carbon-6π-electrocyclization, for rapid and divergent access to dihydropyridoisoquinoliniums and dihydrobenzoquinolines. Through computation, the high selectivity of aza-electrocyclization in the presence of an appropriate "HCl"source under either thermal conditions or photochemical conditions is shown to result from the favorable kinetics and symmetries of frontier orbitals. We further demonstrated the value of this protocol by the synthesis of several complex pyridinium-containing polyheterocycles, including the two alkaloids berberine and chelerythrine.
- Hu, Tianhui,Hua, Yuhui,Jiang, Xunjin,Qiu, Huijuan,Shen, Yang,Wu, Yifan,Xiong, Jing,Xu, Beibei,Zeng, Zhixiong,Zhang, Yandong
-
supporting information
p. 15585 - 15594
(2020/10/20)
-
- Transition-Metal-Free Desulfinative Cross-Coupling of Heteroaryl Sulfinates with Grignard Reagents
-
A mild cross-coupling reaction of heteroaryl sulfinates with Grignard reagents has been developed under transition-metal-free conditions. This study provides an example of the SO22- as a leaving group in an aromatic system and an effective methodology for the construction of C-C bond.
- Wei, Jun,Liang, Huamin,Ni, Chuanfa,Sheng, Rong,Hu, Jinbo
-
-
- Cobalt-Catalyzed Formation of 2-Pyridylzinc Reagents and Their Subsequent Coupling
-
The preparation of pyridylzinc compounds from the corresponding pyridyl halides using a cobalt catalyst is described. The complex employed features a polydentate N-heterocyclic ligand and allows the reaction to be carried out in the absence of pyridine as
- Linke, Stephanie,Manolikakès, Sofia M.,Auffrant, Audrey,Gosmini, Corinne
-
p. 2595 - 2600
(2018/06/08)
-
- Palladium-Catalyzed Decarbonylative Cross-Coupling of Azinecarboxylates with Arylboronic Acids
-
The first palladium-catalyzed decarbonylative coupling of phenyl 2-azinecarboxylates and arylboronic acids is presented. The key for the development of this decarbonylative coupling is the use of Pd/dcype as a catalyst. A wide range of 2-azinecarboxylates can undergo the present coupling reaction to afford 2-arylazines. By combination with previously reported nickel-catalyzed decarbonylative coupling, we achieved a chemoselective sequential decarbonylative coupling of pyridine dicarboxylate to synthesize 2,4-diarylpyridine.
- Muto, Kei,Hatakeyama, Taito,Itami, Kenichiro,Yamaguchi, Junichiro
-
p. 5106 - 5109
(2016/10/14)
-
- Decarboxylative Trifluoromethylating Reagent [Cu(O2CCF3)(phen)] and Difluorocarbene Precursor [Cu(phen)2][O2CCF2Cl]
-
This article describes the new economic decarboxylative trifluoromethylating reagent [Cu(phen)(O2CCF3)] (1; phen=1,10-phenanthroline) and the efficient difluorocarbene precursor [Cu(phen)2][O2CCF2Cl] (2). Treatment of copper tert-butoxide with phen and subsequent addition of trifluoroacetic acid or chlorodifluoroacetic acid afforded air-stable complexes 1 and 2, respectively, which were characterized by X-ray crystallography. The copper(I) ion in 1 is coordinated by a bidentate phen ligand, a monodentate trifluoroacetate group, and a molecule of CH3CN in a distorted tetrahedral coordination geometry. The molecular structure of 2 adopts an ionic form that consists of a [Cu(phen)2]+ cation and a chlorodifluoroacetate anion. Complex 1 reacted with a variety of aryl and heteroaryl halides to form trifluoromethyl (hetero)arenes in good yields. The corresponding Hammett plot exhibited a linear relationship and a reaction parameter (ρ)=+0.56±0.02, which indicated that the trifluoromethylation reaction proceeded via a nucleophilic reactive species. Complex 2 reacts with phenols to produce aryl difluoromethyl ethers in modest-to-excellent yields. Mechanistic investigations revealed that the difluoromethylation reaction proceeds by initial copper-mediated formation of difluorocarbene and subsequent concerted addition of difluorocarbene to the phenol to form a three-center transition state.
- Lin, Xiaoxi,Hou, Chuanqi,Li, Haohong,Weng, Zhiqiang
-
supporting information
p. 2075 - 2084
(2016/02/12)
-
- Based on pyridine ring metal-ligand-platinum complex and its preparation method and application
-
The invention relates to a novel cyclometal ligand-platinum complex and a preparation method and application thereof, and belongs to the technical field of electronic materials. The novel cyclometal ligand-platinum complex is convenient in template design and easy to obtain. Triphenylaminyl, quinolyl and trifluoromethyl are introduced in a material, and the electron structure and the hole injection and transmission performance of the material can be conveniently adjusted by adjusting substituents on an aza heteroaromatic ring. The complex provided by the invention is good in thermal stability and hole injection and transmission performance, and has wide application prospect in the fields of organic electroluminescent materials, oxygen sensing materials, dyes and medicines and the like. The oxygen sensor prepared by the complex has the advantages of simple structure, low cost, reliable work and the like; and the complex can be prepared into a portable oxygen sensor to be popularized and used.
- -
-
Paragraph 0075
(2016/11/07)
-
- Room-temperature palladium-catalysed Suzuki-Miyaura coupling of arylboric acid with aryl chlorides
-
An efficient room-temperature Pd-catalyzed Suzuki-Miyaura cross-coupling reaction of aryl-boronic acids with aryl chlorides is communicated here. The Pd(OAc)2/NiXantphos catalyst system enables the coupling reaction at room temperature in good
- Wang, Dan,Chen, Hong-Guan,Tian, Xin-Chuan,Liang, Xiao-Xia,Chen, Feng-Zhen,Gao, Feng
-
p. 107119 - 107122
(2016/01/08)
-
- A general solution for the 2-pyridyl problem
-
Problem solved: An air-stable 2-pyridyl borane that can effectively couple to a wide range of aryl and heteroaryl halides and pseudohalides has evaded the synthesis community for decades. The discovery that Cu(DEA)2 powerfully enables palladium-mediated cross-couplings with air-stable boronates 1 has finally provided a general solution to this problem. DEA=diethanolamine, DMF=N,N′-dimethylformamide, Tf=trifluoromethanesulfonyl. Copyright
- Dick, Graham R.,Woerly, Eric M.,Burke, Martin D.
-
supporting information; experimental part
p. 2667 - 2672
(2012/04/23)
-
- Negishi cross-coupling reactions catalyzed by an aminophosphine-based nickel system: A reliable and general applicable reaction protocol for the high-yielding synthesis of biaryls
-
Treatment of NMP solutions of NiCl2 with 1,1′,1″- (phosphanetriyl)tripiperidine (≈2.05 equiv), dissolved in THF, in air at 25°C forms a highly active catalytic system for the cross-coupling of a large variety of electronically activated, non-activated, deactivated, and ortho-substituted, heterocyclic, and functionalized aryl bromides and aryl chlorides with diarylzinc reagents. Very high levels of conversion and yields were obtained within 2 h at 60°C in the presence of only 0.1 mol% of catalyst (based on nickel) and thus at catalyst loadings far lower than typically reported for nickel-catalyzed versions of the Negishi reaction. Various aryl halides-which may contain trifluoromethyl groups, fluorides, or other functional groups such as acetals, ketones, ethers, esters, lactones, amides, imines, anilines, alkenes, pyridines, quinolines, and pyrimidines-were successfully converted into the corresponding biaryls. Electronic and steric variations are tolerated in both reaction partners. Experimental observations indicate that a molecular (NiI/NiIII) mechanism is operative.
- Gerber, Roman,Frech, Christian M.
-
experimental part
p. 11893 - 11904
(2011/11/29)
-
- Luminescent cyclometalated dialkynylgold(III) complexes of 2-phenylpyridine-type derivatives with readily tunable emission properties
-
A novel class of luminescent dialkynylgold(III) complexes containing various phenylpyridine and phenylisoquinoline-type bidentate ligands has been successfully synthesized and characterized. The structures of some of them have also been determined by X-ray crystallography. Electrochemical studies demonstrate the presence of a ligand-centered reduction originating from the cyclometalating C^N ligand, whereas the first oxidation wave is associated with an alkynyl ligand-centered oxidation. The electronic absorption and photoluminescence properties of the complexes have also been investigated. In dichloromethane solution at room temperature, the low-energy absorption bands are assigned as the metal-perturbed π-π* intraligand (IL) transition of the cyclometalating C^N ligand, with mixing of charge-transfer character from the aryl ring to the pyridine or isoquinoline moieties of the cyclometalating C^N ligand. The low-energy emission bands of the complexes in fluid solution at room temperature are ascribed to originate from the metal-perturbed π-π* IL transition of the cyclometalatng C^N ligand. For complex 4 that contains an electron-rich amino substituent on the alkynyl ligand, a structureless emission band, instead of one with vibronic structures as in the other complexes, was observed, which was assigned as being derived from an excited state of a [π(Ci£CC6H 4NH2)→π (C^N)] ligand-to-ligand charge-transfer (LLCT) transition. Luminescence enhancement: A novel class of luminescent dialkynylgold(III) complexes containing various phenylpyridine- and phenylisoquinoline-type bidentate ligands has been successfully synthesized and characterized. This class of complexes has been shown to demonstrate rich and tunable photoluminescence properties (see picture).
- Au, Vonika Ka-Man,Wong, Keith Man-Chung,Zhu, Nianyong,Yam, Vivian Wing-Wah
-
experimental part
p. 130 - 142
(2011/03/21)
-
- Pd-catalyzed cross-coupling of functionalized organozinc reagents with thiomethyl-substituted heterocycles
-
Various thiomethyl-substituted N-heterocycles (pyridines, pyrimidines, pyrazines, pyridazines, triazines, benzothiazoles, benzoxazoles, pyrazoles, benzindazoles, quinazolines, etc.) undergo smooth Pd-catalyzed cross-coupling reactions with functionalized
- Metzger, Albrecht,Melzig, Laurin,Despotopoulou, Christina,Knochel, Paul
-
supporting information; experimental part
p. 4228 - 4231
(2009/12/07)
-
- Synthesis of functionalized 2-arylpyridines from 2-halopyridines and various aryl halides via a nickel catalysis
-
An efficient nickel-catalyzed method devoted to the direct formation of functionalized 2-arylpyridines is described avoiding the prior preparation of organometallic species. Various functionalized 2-arylpyridines are obtained in moderate to excellent yields by a one-step chemical procedure from corresponding halides. The NiBr2(2,2′-bipyridine) complex appears to be an extremely suitable catalyst for the activation in the presence of manganese dust of aromatic halides and pyridyl halides functionalized by reactive groups. The versatility of this original process represents a simple alternative to most known methods using organometallic reagents.
- Gosmini, Corinne,Bassene-Ernst, Carine,Durandetti, Muriel
-
experimental part
p. 6141 - 6146
(2011/03/19)
-
- Electrosynthesis of functionalized 2-arylpyridines from functionalized aryl and pyridine halides catalyzed by nickel bromide 2,2'-bipyridine complex
-
2-Arylpyridines substituted on aryl and/or on pyridine nuclei can be obtained in good to high yields in one step by electroreduction of mixtures of the corresponding aryl and pyridyl halides using the sacrificial iron anode process and a nickel 2,2'-bipyr
- Gosmini, Corinne,Nédélec, Jean Yves,Périchon, Jacques
-
p. 5039 - 5042
(2007/10/03)
-
- Electrochemical cross-coupling between 2-halopyridines and aryl or heteroaryl halides catalysed by nickel-2,2'-bipyridine complexes
-
2-Arylpyridines can be obtained in good to high yields by electrochemical reductin using the sacrificial anode process and catalysis by nickel-2,2'-bipyridine (bpy) complexes. In a first approach functionalized arylzinc species are prepared in DMF as solvent by electrolytic reduction of the corresponding aryl-bromides or -chlorides in the presence of ZnBr2 and Ni(II)-bpy complexes and then coupled with 2-chloropyridine. In a second approach the cross-coupling occurs from the electrochemical reduction of a stoichiometric mixture of an aryl halide and 2-halopyridine in DMF in the presence of NiBr2bpy as catalyst.
- Gosmini, Corinne,Lasry, Sarah,Nedelec, Jean-Yves,Perichon, Jacques
-
p. 1289 - 1298
(2007/10/03)
-