Bathocuproine-Enabled Nickel-Catalyzed Selective Ullmann Cross-Coupling of Two sp2-Hybridized Organohalides

Synlett ◽  
2021 ◽  
Vol 32 (16) ◽  
pp. 1657-1661
Author(s):  
Yuqiang Li ◽  
Guoyin Yin
Keyword(s):  
Functional Groups ◽  
Organic Molecules ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Reaction Conditions ◽  
Cross Coupling Reactions ◽  
Wide Range ◽  
Complex Organic

AbstractCross-coupling reactions are essential for the synthesis of complex organic molecules. Here, we report a nickel-catalyzed Ullmann cross-coupling of two sp2-hybridized organohalides, featuring high cross-selectivity when the two coupling partners are used in a 1:1 ratio. The high chemoselectivity is governed by the bathocuproine ligand. Moreover, the mild reductive reaction conditions allow that a wide range of functional groups are compatible in this Ullmann cross-coupling.

PdII Immobilized on Ferromagnetic Multi-Walled Carbon Nanotubes Functionalized by Aminated 2-Chloroethylphosphonic Acid with S-Methylisothiourea (FMMWCNTs@CPA@SMTU@PdII NPs) Applied as a Highly Efficient and Recyclable Nanostructured Catalyst for Suzuki–Miyaura and Mizoroki–Heck Cross-Coupling Reactions in Solvent-Free Conditions

2019 ◽  
Vol 72 (9) ◽  
pp. 674 ◽  
Author(s):  
Maryam Sadat Ghasemzadeh ◽  
Batool Akhlaghinia
Keyword(s):  
Catalytic Activity ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Reaction Conditions ◽  
Cross Coupling Reactions ◽  
Solvent Free Conditions ◽  
Wide Range ◽  
Multi Walled Carbon Nanotubes ◽  
Catalyst Reusability ◽  
Walled Carbon Nanotubes

The new ferromagnetic nanostructured FMMWCNTs@CPA@SMTU@PdII NPs (IV) as an eco-friendly heterogeneous nanocatalyst with a particle size of ~20–30nm reported earlier by our group has been found to be very effective for Suzuki–Miyaura and Mizoroki–Heck cross-coupling reactions at ambient temperature. The procedure has been applied for a wide range of aryl halides, arylboronic acids, and alkenes. The magnetic separation by an external magnetic field, mild reaction conditions, and catalyst reusability up to four times without significant decrease in catalytic activity (reduced catalytic activity from 11 to 18% in the fifth, sixth, and seventh cycles) made the present method sustainable and economically viable for C–C cross-coupling reactions.

scholarly journals POxAP Precatalysts and the Negishi Cross-Coupling Reaction

Synthesis ◽  
2019 ◽  
Vol 52 (01) ◽  
pp. 51-59
Author(s):  
Shuang-Qi Tang ◽  
Martine Schmitt ◽  
Frédéric Bihel
Keyword(s):  
Functional Groups ◽  
Oxidative Addition ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Catalytic Activities ◽  
Cross Coupling Reactions ◽  
Cross Coupling Reaction ◽  
Wide Range ◽  
Organozinc Reagents

Recently developed for the Fukuyama reaction, post-oxidative addition precatalysts (POxAPs) are also very efficient in catalyzing Negishi cross-coupling reactions between organohalides and organozinc reagents. Using very low catalyst loadings, POxAPs show similar catalytic activities to those of classical precatalysts such as XPhos Pd G4 or PEPPSI-IPr, with turnover numbers of up to 93,000. POxAPs are easily prepared, are stable to air and moisture, tolerate a wide range of functional groups in the Negishi cross-coupling reaction and contribute advantageously to the arsenal of organic chemists in terms of Pd precatalysts.

scholarly journals A novel 4-aminoantipyrine-Pd(II) complex catalyzes Suzuki–Miyaura cross-coupling reactions of aryl halides

2014 ◽  
Vol 10 ◽  
pp. 2821-2826 ◽  
Author(s):  
Claudia Araceli Contreras-Celedón ◽  
Darío Mendoza-Rayo ◽  
José A Rincón-Medina ◽  
Luis Chacón-García
Keyword(s):  
Functional Groups ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
Aryl Halides ◽  
Coupling Reactions ◽  
Reaction Conditions ◽  
Cross Coupling Reactions ◽  
Highly Active ◽  
Cross Coupling Reaction ◽  
Phenylboronic Acids

A simple and efficient catalytic system based on a Pd complex of 4-aminoantipyrine, 4-AAP–Pd(II), was found to be highly active for Suzuki–Miyaura cross-coupling of aryl iodides and bromides with phenylboronic acids under mild reaction conditions. Good to excellent product yields from the cross-coupling reaction can be achieved when the reaction is carried out in ethanol, in the open air, using low loading of 4-AAP–Pd(II) as a precatalyst, and in the presence of aqueous K2CO3 as the base. A variety of functional groups are tolerated.

Carbon-Heteroatom Cross-Coupling via an Electronically Excited Nickel (II) Complex

2019 ◽  
Author(s):  
Randolph Escobar ◽  
Jeffrey Johannes
Keyword(s):  
Energy Transfer ◽  
Functional Groups ◽  
Cross Coupling ◽  
Reductive Elimination ◽  
Aryl Halides ◽  
Coupling Reactions ◽  
General Methodology ◽  
Cross Coupling Reactions ◽  
Electronically Excited ◽  
Energy Transfer Pathway

<div>While carbon-heteroatom cross coupling reactions have been extensively studied, many methods are specific and</div><div>limited to a set of substrates or functional groups. Reported here is a method that allows for C-O, C-N and C-S cross coupling reactions under one general methodology. We propose that an energy transfer pathway, in which an iridium photosensitizer produces an excited nickel (II) complex, is responsible for the key reductive elimination step that couples aryl halides to 1° and 2° alcohols, anilines, thiophenols, carbamates and sulfonamides.</div>

Monodentate Trialkylphosphines: Privileged Ligands in Metal-catalyzed Crosscoupling Reactions

2020 ◽  
Vol 24 (3) ◽  
pp. 231-264 ◽  
Author(s):  
Kevin H. Shaughnessy
Keyword(s):  
Transition Metal ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Cross Coupling Reactions ◽  
Aryl Bromides ◽  
Wide Range ◽  
Sterically Demanding ◽  
Transition Metal Catalyzed ◽  
Catalyzed Reactions ◽  
Metal Catalyzed

Phosphines are widely used ligands in transition metal-catalyzed reactions. Arylphosphines, such as triphenylphosphine, were among the first phosphines to show broad utility in catalysis. Beginning in the late 1990s, sterically demanding and electronrich trialkylphosphines began to receive attention as supporting ligands. These ligands were found to be particularly effective at promoting oxidative addition in cross-coupling of aryl halides. With electron-rich, sterically demanding ligands, such as tri-tertbutylphosphine, coupling of aryl bromides could be achieved at room temperature. More importantly, the less reactive, but more broadly available, aryl chlorides became accessible substrates. Tri-tert-butylphosphine has become a privileged ligand that has found application in a wide range of late transition-metal catalyzed coupling reactions. This success has led to the use of numerous monodentate trialkylphosphines in cross-coupling reactions. This review will discuss the general properties and features of monodentate trialkylphosphines and their application in cross-coupling reactions of C–X and C–H bonds.

Comparison of the Suzuki cross-coupling reactions of 4,7-dichloroquinoline and 7-chloro-4-iodoquinoline with arylboronic acids using phosphine-free palladium catalysis in water

2004 ◽  
Vol 82 (2) ◽  
pp. 206-214 ◽  
Author(s):  
Richard W Friesen ◽  
Laird A Trimble
Keyword(s):  
Phenylboronic Acid ◽  
Palladium Catalysis ◽  
Suzuki Reaction ◽  
Tetrabutylammonium Bromide ◽  
Cross Coupling ◽  
Palladium Acetate ◽  
Coupling Reactions ◽  
Reaction Conditions ◽  
Arylboronic Acids ◽  
Cross Coupling Reactions

4,7-Dichloroquinoline (1a) and 7-chloro-4-iodoquinoline (1b) undergo Suzuki cross-coupling reactions with arylboronic acids catalyzed by phosphine-free palladium acetate in boiling water. Using phenylboronic acid (2), the reaction of 1a provides 7-chloro-4-phenylquinoline (3) (78%) together with diphenylquinoline (4) (12%), while 1b reacts in a much more regioselective fashion and provides 3 in 98% isolated yield. Although 1b undergoes a more regioselective Suzuki reaction than 1a, additional important observations are that the overall reaction of 1b with 2 is three times slower than 1a and that the reaction occurs in the absence of tetrabutylammonium bromide. Using optimized reaction conditions, a variety of aryl and vinylboronic acids undergo regioselective Suzuki cross-coupling with 1b to provide the products 7, 10, and 11 in good to excellent yield.Key words: palladium, cross-coupling, regioselectivity, quinolines, boronic acids.

scholarly journals Synthesis of 9-arylalkynyl- and 9-aryl-substituted benzo[b]quinolizinium derivatives by Palladium-mediated cross-coupling reactions

2018 ◽  
Vol 14 ◽  
pp. 1871-1884 ◽  
Author(s):  
Siva Sankar Murthy Bandaru ◽  
Darinka Dzubiel ◽  
Heiko Ihmels ◽  
Mohebodin Karbasiyoun ◽  
Mohamed M A Mahmoud ◽  
...  
Keyword(s):  
Emission Intensity ◽  
Binding Constants ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Sonogashira Coupling ◽  
Reaction Conditions ◽  
Quadruplex Dna ◽  
Cross Coupling Reactions ◽  
Sonogashira Coupling Reaction

9-Arylbenzo[b]quinolizinium derivatives were prepared with base-free Suzuki–Miyaura coupling reactions between benzo[b]quinolizinium-9-trifluoroborate and selected benzenediazonium salts. In addition, the Sonogashira coupling reaction between 9-iodobenzo[b]quinolizinium and the arylalkyne derivatives yielded four novel 9-(arylethynyl)benzo[b]quinolizinium derivatives under relatively mild reaction conditions. The 9-(N,N-dimethylaminophenylethynyl)benzo[b]quinolizinium is only very weakly emitting, but the emission intensity increases by a factor >200 upon protonation, so that this derivative may operate as pH-sensitive light-up probe. Photometric and fluorimetric titrations of duplex and quadruplex DNA to 9-(arylethynyl)benzo[b]quinolizinium derivatives revealed a significant binding affinity of these compounds towards both DNA forms with binding constants ofKb= 0.2–2.2 × 105M−1.

Regiospecific Palladium-Catalyzed Cross-Coupling Reactions Using the Operational Equivalent of 1,3-Dilithiopropyne

Synthesis ◽  
2020 ◽  
Vol 52 (16) ◽  
pp. 2387-2394 ◽  
Author(s):  
Jorge A. Cabezas ◽  
Natasha Ferllini
Keyword(s):  
Coupling Reaction ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Terminal Alkyne ◽  
Copper Iodide ◽  
Reaction Conditions ◽  
Cross Coupling Reactions ◽  
Cross Coupling Reaction ◽  
Palladium Catalyzed ◽  
High Yields

A regiospecific palladium-catalyzed cross-coupling reaction using the operational equivalent of the dianion 1,3-dilithiopropyne, with aromatic iodides is reported. This reaction gives high yields of 1-propyn-1-yl-benzenes and 2-(propyn-1-yl)thiophenes in the presence of catalytic amounts of palladium(0) or (II) and stoichiometric amounts of copper iodide. No terminal alkyne or allene isomers were detected. Reaction conditions were very mild and several functional groups were tolerated.

A novel and efficient zinc-catalyzed thioetherification of aryl halides

RSC Advances ◽  
2015 ◽  
Vol 5 (41) ◽  
pp. 32675-32678 ◽  
Author(s):  
Amrutha P. Thankachan ◽  
K. S. Sindhu ◽  
K. Keerthi Krishnan ◽  
Gopinathan Anilkumar
Keyword(s):  
Cross Coupling ◽  
Aryl Halides ◽  
Coupling Reactions ◽  
Reaction Conditions ◽  
Cross Coupling Reactions

The first Zn-catalyzed protocol for C–S cross-coupling reactions for the synthesis of substituted aryl and alkyl sulfides with good yields under mild reaction conditions is described.

Copper-catalyzed synthesis of 2-aminophenyl benzothiazoles: a novel approach

2018 ◽  
Vol 16 (37) ◽  
pp. 8267-8272 ◽  
Author(s):  
S. N. Murthy Boddapati ◽  
Chandra Mohan Kurmarayuni ◽  
Baby Ramana Mutchu ◽  
Ramana Tamminana ◽  
Hari Babu Bollikolla
Keyword(s):  
Nucleophilic Substitution ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Reaction Conditions ◽  
Moderate Reaction ◽  
Cross Coupling Reactions ◽  
Novel Approach

Substituted 2-aminophenyl benzothiazoles have been constructed from thiourea via copper-catalyzed desulfurization/nucleophilic substitution followed by domino intra- and intermolecular C–N cross-coupling reactions under moderate reaction conditions.

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