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

2021 ◽  
Vol 12 (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.

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

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.

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

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.

Chiral Mn(III) Salen Complex Immobilized on CuFe2O4@SiO2-NH2 NPs: A Cheap and Efficient Catalyst for N-arylation of Aryl Halides and Phenylboronic Acid Under Mild Conditions

2020 ◽  
Vol 17 (11) ◽  
pp. 857-863
Author(s):  
Mohammad Ali Nasseri ◽  
Seyyedeh Ameneh Alavi ◽  
Milad Kazemnejadi ◽  
Ali Allahresani
Keyword(s):  
Phenylboronic Acid ◽  
Significant Loss ◽  
Aryl Halides ◽  
Coupling Reactions ◽  
Efficient Catalyst ◽  
Aryl Chlorides ◽  
Mild Conditions ◽  
Cross Coupling Reactions ◽  
Salen Complex ◽  
Ft Ir

A convenient and efficient chiral CuFe2O4@SiO2-Mn(III) Ch.salen nanocatalyst has been developed for the C-N cross-coupling reactions of aryl halides/ phenylboronic acid with N-heterocyclic compounds in water and/or DMSO under mild conditions. The catalyst could be applied for the N-arylation of a variety of nitrogen-containing heterocycles with aryl chlorides, bromides, iodides and phenylboronic acid under mild conditions. Moderate to good yields were achieved for all substrates. The structure of catalyst was characterized using various techniques including FT-IR, FE-SEM, EDX, XRD, TEM and TGA. The catalyst can be simply recovered and reused for several times without significant loss of activity.

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

Synlett ◽  
2017 ◽  
Vol 28 (11) ◽  
pp. 1258-1267 ◽  
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

scholarly journals Photochemically-Mediated Nickel-Catalyzed Synthesis of N-(Hetero)aryl Sulfamides

2020 ◽  
Author(s):  
Robert Simons ◽  
Georgia Scott ◽  
Anastasia Gant Kanegusuku ◽  
Jennifer Roizen
Keyword(s):  
Visible Light ◽  
Catalytic System ◽  
Visible Light Irradiation ◽  
Room Temperature ◽  
Iridium Complex ◽  
Aryl Chlorides ◽  
Coupling Methods ◽  
Aryl Bromides ◽  
Boronic Esters ◽  
General Method

A general method for the <i>N</i>-arylation of sulfamides with aryl bromides is described. The protocol leverates a dual-catalytic system of nickel and a photoexcitable iridium complex and proceeds at room temperature under visible light irradiation. Using these tactics, aryl boronic esters and aryl chlorides can be carried through the reaction untouched. Thereby, this method complements known Buchwald-Hartwig coupling methods for N-arylation of sulfamides.

scholarly journals Synthesis of Stereodefined 1,1-Diborylalkenes via Copper-Catalyzed Diboration of Terminal Alkynes

2020 ◽  
Author(s):  
Yang Gao ◽  
Zhong-Qian Wu ◽  
Keary Engle
Keyword(s):  
Functional Group ◽  
Aryl Halides ◽  
Terminal Alkynes ◽  
Mild Conditions ◽  
Tandem Process ◽  
Trisubstituted Alkenes

A copper-catalyzed method for the <i>E</i>-selective 1,1-diboration of terminal alkynes is described. The tandem process involves sequential dehydrogenative borylation of the alkyne substrate with HBdan (HBdan = 1,8-diaminonaphthalatoborane), followed by hydroboration with HBpin (HBpin = pinacolborane). This method proceeds efficiently under mild conditions, furnishing 1,1-diborylalkenes with excellent stereoselectivity and broad functional-group tolerance. Taking advantage of the different reactivities of the two boryl moieties, the products can then be employed in stepwise cross-couplings with aryl halides for the stereocontrolled construction of trisubstituted alkenes.

Fe(III)/l-Valine-Catalyzed One-Pot Synthesis of N-Sulfinyl- and N-Sulfonylimines via Oxidative Cascade Reaction of Alcohols with Sulfinamides or Sulfonamides

Synlett ◽  
2018 ◽  
Vol 29 (09) ◽  
pp. 1232-1238
Author(s):  
Guofu Zhang ◽  
Yunzhe Xing ◽  
Shengjun Xu ◽  
Chengrong Ding ◽  
Shang Shan
Keyword(s):  
Catalytic System ◽  
Functional Group ◽  
Cascade Reaction ◽  
One Pot ◽  
Mild Conditions ◽  
One Pot Synthesis ◽  
Oxidation Of Alcohols

An efficient Fe(III), l-valine, and 4-OH-TEMPO catalytic system was found for the oxidation of alcohols followed by condensation with sulfinamide or sulfonamide in one pot for the synthesis of N-sulfinyl- and N-sulfonylimines compounds under mild conditions. This transformation accommodates a variety of substrates, shows high functional-group tolerance, and affords the corresponding products in good to excellent yields.

Visible-Light-Driven Reductive Carboarylation of Styrenes with CO2 and Aryl Halides

2019 ◽  
Author(s):  
Hao Wang ◽  
yuzhen gao ◽  
Chunlin Zhou ◽  
Gang Li
Keyword(s):  
Visible Light ◽  
Alkyl Halides ◽  
Aryl Halides ◽  
Addition Reactions ◽  
Aryl Chlorides ◽  
Aryl Iodides ◽  
Visible Light Driven ◽  
User Friendly

The first example of visible-light-driven reductive carboarylation of styrenes with CO<sub>2</sub> and aryl halides in a regioselective manner has been achieved. A broad range of aryl iodides and bromides were compatible with this reaction. <a>Moreover, pyridyl halides, alkyl halides and even aryl chlorides were also viable with this method.</a> These findings may stimulate the exploration of novel visible-light-driven Meerwein arylation-addition reactions with user-friendly aryl halides as the radical sources and the photocatalytic utilization of CO<sub>2.</sub>

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

Synlett ◽  
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.

scholarly journals A Widely Applicable Dual-Catalytic System for Cross-Electrophile Coupling

2020 ◽  
Author(s):  
David Charboneau ◽  
Emily L. Barth ◽  
Nilay Hazari ◽  
Mycah R. Uehling ◽  
Susan L. Zultanski
Keyword(s):  
Catalytic System ◽  
Aryl Halide ◽  
Alkyl Halides ◽  
Aryl Halides ◽  
Ni Catalyst ◽  
Similar Reaction ◽  
Coupling Reactions ◽  
One Pot ◽  
Diverse Range ◽  
Co Catalyst

A new dual catalytic system for cross-electrophile coupling reactions between aryl and alkyl halides that features a Ni catalyst, a Co co-catalyst, and a mild homogeneous reductant, is described. This is a unique combination of reagents for cross-electrophile coupling reactions, which results in one of the most versatile systems reported to date. For example, the coupling of aryl bromides and aryl iodides with alkyl bromides, alkyl iodides, alkyl mesylates, and benzyl chlorides is demonstrated under similar reaction conditions. The system is tolerant of numerous functional groups and is capable of coupling heteroaryl halides, di-ortho-substituted aryl halides, pharmaceutically relevant drug-like aryl halides, and a diverse range of alkyl halides. Additionally, the dual catalytic platform facilitates a series of novel one-pot three-component cross-electrophile coupling reactions of bromo(iodo)arenes with two distinct alkyl halides. Mechanistic studies indicate that the Ni catalyst activates the aryl halide electrophile, while the Co catalyst activates the alkyl electrophile.

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