Nickel-Catalyzed Ligand-Free Hiyama Coupling of Aryl Bromides and Vinyltrimethoxysilane

A novel decarboxylative N-arylation of indole-2-carboxylic acids with aryl halides is developed. The reaction proceeds efficiently in the presence of Cu2O as the catalyst to give the corresponding N-aryl indoles in high yields. This synthetic method shows good functional group tolerance and offers an alternative route to construct N-aryl indoles.

Download Full-text

Cu(i) catalysis for selective condensation/bicycloaromatization of two different arylalkynes: direct and general construction of functionalized C–N axial biaryl compounds

Chemical Science ◽

10.1039/d1sc03865f ◽

2022 ◽

Author(s):

Qian Shang ◽

Haifang Tang ◽

Yongping Liu ◽

MingMing Yin ◽

Lebin Su ◽

...

Keyword(s):

Functional Group ◽

Direct Synthesis ◽

General Construction ◽

Ligand Free ◽

High Yields ◽

Excellent Selectivity ◽

Biaryl Compounds

Selective condensation/bicycloaromatization of two different arylalkynes is firstly developed under ligand-free copper(i)-catalysis, which allows the direct synthesis of C–N axial biaryl compounds in high yields with excellent selectivity and functional group tolerance.

Download Full-text

Copper(II)-Catalyzed C–N Coupling of Aryl Halides and N-Nucleophiles Promoted by Quebrachitol or Diethylene Glycol

Synlett ◽

10.1055/s-0039-1690707 ◽

2019 ◽

Vol 30 (19) ◽

pp. 2161-2168

Author(s):

Fangyu Du ◽

Qifan Zhou ◽

Yang Fu ◽

Yuanguang Chen ◽

Ying Wu ◽

...

Keyword(s):

Diethylene Glycol ◽

Functional Group ◽

Aryl Halides ◽

Coupling Reactions ◽

Mild Conditions ◽

Natural Ligand ◽

Highly Effective ◽

High Yields

Herein, we report the natural ligand quebrachitol (QCT) as a promoter for a Cu(II) catalyst, which is highly effective for N-arylation of various amines and related aryl halides. A series of diarylamine derivatives were obtained in high yields by using diethylene glycol (DEG) as both ligand and solvent. The C–N coupling reactions proceed under mild conditions and exhibit good functional group tolerance.

Download Full-text

Nickel-catalyzed electrochemical carboxylation of unactivated aryl and alkyl halides with CO2

Nature Communications ◽

10.1038/s41467-021-27437-8 ◽

2021 ◽

Vol 12 (1) ◽

Cited By ~ 1

Author(s):

Guo-Quan Sun ◽

Wei Zhang ◽

Li-Li Liao ◽

Li Li ◽

Zi-Hao Nie ◽

...

Keyword(s):

Catalytic System ◽

Functional Group ◽

Alkyl Halides ◽

Aryl Halides ◽

Aryl Chlorides ◽

Mild Conditions ◽

Aryl Bromides ◽

Alkyl Bromides ◽

Pseudo Halides ◽

Electrochemical Carboxylation

AbstractElectrochemical catalytic reductive cross couplings are powerful and sustainable methods to construct C−C bonds by using electron as the clean reductant. However, activated substrates are used in most cases. Herein, we report a general and practical electro-reductive Ni-catalytic system, realizing the electrocatalytic carboxylation of unactivated aryl chlorides and alkyl bromides with CO2. A variety of unactivated aryl bromides, iodides and sulfonates can also undergo such a reaction smoothly. Notably, we also realize the catalytic electrochemical carboxylation of aryl (pseudo)halides with CO2 avoiding the use of sacrificial electrodes. Moreover, this sustainable and economic strategy with electron as the clean reductant features mild conditions, inexpensive catalyst, safe and cheap electrodes, good functional group tolerance and broad substrate scope. Mechanistic investigations indicate that the reaction might proceed via oxidative addition of aryl halides to Ni(0) complex, the reduction of aryl-Ni(II) adduct to the Ni(I) species and following carboxylation with CO2.

Download Full-text

Enantioselective alpha-Arylation of Benzamides via Synergistic Nickel and Metallaphotoredox Catalysis

10.26434/chemrxiv.9978824.v1 ◽

2019 ◽

Author(s):

John Montgomery ◽

Alexander W. Rand

Keyword(s):

Catalytic System ◽

Functional Group ◽

Enantiomeric Excess ◽

New Method ◽

Aryl Bromides

A new method to access alpha-arylated benzamides has been enabled by metallaphotoredox catalysis. This system allows for non-directed C–H functionalization of N-alkyl benzamides using a dual nickel/iridium catalytic system to form tertiary stereocenters in good enantiomeric excess and moderate yields. This reaction shows excellent functional group compatibility and can be performed using a number of sterically and electronically different aryl bromides and secondary benzamides.

Download Full-text

Enantioselective alpha-Arylation of Benzamides via Synergistic Nickel and Metallaphotoredox Catalysis

10.26434/chemrxiv.9978824 ◽

2019 ◽

Author(s):

John Montgomery ◽

Alexander W. Rand

Keyword(s):

Catalytic System ◽

Functional Group ◽

Enantiomeric Excess ◽

New Method ◽

Aryl Bromides

A new method to access alpha-arylated benzamides has been enabled by metallaphotoredox catalysis. This system allows for non-directed C–H functionalization of N-alkyl benzamides using a dual nickel/iridium catalytic system to form tertiary stereocenters in good enantiomeric excess and moderate yields. This reaction shows excellent functional group compatibility and can be performed using a number of sterically and electronically different aryl bromides and secondary benzamides.

Download Full-text

An Efficient Synthesis of 2-Substituted Quinazolin-4(3H)-ones by Using Recyclable Wang Resin Supported Sulfonic Acid Catalyst

Letters in Organic Chemistry ◽

10.2174/1570178617999201109203731 ◽

2020 ◽

Vol 17 ◽

Author(s):

Kalyani K. ◽

Srinivasa Reddy Kallam

Keyword(s):

Sulfonic Acid ◽

Functional Group ◽

Acid Catalyst ◽

Sulphonic Acid ◽

Isatoic Anhydride ◽

Efficient Synthesis ◽

Wang Resin ◽

Polymer Supported ◽

High Yields

Abstract:: An efficient synthesis of 2-substituted Quinazolin-4(3H)-ones has been developed from isatoic anhydride with various amidoximes by using recyclable polymer supported sulphonic acid catalyst. Excellent functional group compatibil-ity and high yields are the important features of this protocol.

Download Full-text

A copper nitride catalyst for the efficient hydroxylation of aryl halides under ligand-free conditions

Organic & Biomolecular Chemistry ◽

10.1039/d1ob00768h ◽

2021 ◽

Author(s):

Hang Xu ◽

Sho Yamaguchi ◽

Takato Mitsudome ◽

Tomoo Mizugaki

Keyword(s):

Catalytic Activity ◽

Heterogeneous Catalyst ◽

Aryl Halides ◽

High Catalytic Activity ◽

Copper Nitride ◽

Ligand Free

Copper nitride (Cu3N) was used as a heterogeneous catalyst for the hydroxylation of aryl halides under ligand-free conditions. The cubic Cu3N nanoparticles showed high catalytic activity, comparable to those of...

Download Full-text

Transition-Metal-Free Boryl Substitution Using Silylboranes and Alkoxy Bases

Synlett ◽

10.1055/s-0036-1588772 ◽

2017 ◽

Vol 28 (11) ◽

pp. 1258-1267 ◽

Cited By ~ 2

Author(s):

Hajime Ito ◽

Eiji Yamamoto ◽

Satoshi Maeda ◽

Tetsuya Taketsugu

Keyword(s):

Transition Metal ◽

Functional Group ◽

Experimental Studies ◽

Transition Metal Catalysts ◽

Alkyl Halides ◽

Aryl Halides ◽

Nucleophilic Attack ◽

Important Class ◽

Mechanistic Studies ◽

Induced Reaction

Silylboranes are used as borylation reagents for organohalides in the presence of alkoxy bases without transition-metal catalysts. PhMe2Si–B(pin) reacts with a variety of aryl, alkenyl, and alkyl halides, including sterically hindered examples, to provide the corresponding organoboronates in good yields with high borylation/silylation ratios, showing good functional group compatibility. Halogenophilic attack of a silyl nucleophile on organohalides, and subsequent nucleophilic attack on the boron electrophile are identified to be crucial, based on the results of extensive theoretical and experimental studies. This borylation reaction is further applied to the first direct dimesitylboryl (BMes2) substitution of aryl halides using Ph2MeSi–BMes2 and Na(O-t-Bu), affording aryldimesitylboranes, which are regarded as an important class of compounds for organic materials.1 Introduction2 Boryl Substitution of Organohalides with PhMe2Si–B(pin)/Alkoxy Bases3 Mechanistic Investigations4 DFT Mechanistic Studies Using an Artificial Force Induced Reaction (AFIR) Method5 Dimesitylboryl Substitution of Aryl Halides with Ph2MeSi–BMes2/Na(O-t-Bu)6 Conclusion

Download Full-text