Oxidative cross-coupling processes inspired by the Chan–Lam reaction

2021 ◽  
Vol 57 (22) ◽  
pp. 2724-2731
Author(s):  
Michael G. J. Doyle ◽  
Rylan J. Lundgren
Keyword(s):  
Carboxylic Acids ◽  
Oxidative Coupling ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Feature Article ◽  
Boronic Esters ◽  
Oxidative Coupling Reactions ◽  
Coupling Processes

This feature article describes our discovery and application of Cu-catalyzed oxidative coupling reactions of activated methylene derivatives or carboxylic acids with nucleophiles including aryl boronic esters and amines.

Gold Catalyzed Decarboxylative Cross-Coupling of Iodoarenes

2020 ◽  
Author(s):  
Ryan A. Daley ◽  
Joseph Topczewski
Keyword(s):  
Oxidative Coupling ◽  
Field Effect ◽  
Gold Catalyst ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Gold Complexes ◽  
Site Specific ◽  
Effect Parameter ◽  
Oxidative Coupling Reactions

This report details a decarboxylative cross-coupling of (hetero)aryl carboxylates with iodoarenes in the presence of a gold catalyst (>25 examples, up to 96% yield). Generating an aryl nucleophile via decarboxylation obviates problems associated with transmetalation at a putative gold(III) complex. This reaction is site specific, which overcomes prior limitations associated with gold catalyzed oxidative coupling reactions. The reactivity of the (hetero)aryl carboxylate correlates qualitatively to the field effect parameter (Fortho). Furthermore, each step in a proposed mechanism was observed from isolated gold complexes, supporting a gold catalyzed mechanism.

Gold Catalyzed Decarboxylative Cross-Coupling of Iodoarenes

2020 ◽  
Author(s):  
Ryan A. Daley ◽  
Joseph Topczewski
Keyword(s):  
Oxidative Coupling ◽  
Field Effect ◽  
Gold Catalyst ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Gold Complexes ◽  
Site Specific ◽  
Effect Parameter ◽  
Oxidative Coupling Reactions

This report details a decarboxylative cross-coupling of (hetero)aryl carboxylates with iodoarenes in the presence of a gold catalyst (>25 examples, up to 96% yield). Generating an aryl nucleophile via decarboxylation obviates problems associated with transmetalation at a putative gold(III) complex. This reaction is site specific, which overcomes prior limitations associated with gold catalyzed oxidative coupling reactions. The reactivity of the (hetero)aryl carboxylate correlates qualitatively to the field effect parameter (Fortho). Furthermore, each step in a proposed mechanism was observed from isolated gold complexes, supporting a gold catalyzed mechanism.

Recent advances in iodine mediated electrochemical oxidative cross-coupling

2018 ◽  
Vol 16 (14) ◽  
pp. 2375-2387 ◽  
Author(s):  
Kun Liu ◽  
Chunlan Song ◽  
Aiwen Lei
Keyword(s):  
Oxidative Coupling ◽  
Cross Coupling ◽  
Review Article ◽  
Coupling Reactions ◽  
Recent Advances ◽  
Oxidative Coupling Reactions

This review article gives an overview of the recent development of iodine mediated electrochemical oxidative coupling reactions.

scholarly journals Copper catalyzed oxidative coupling reactions for trifluoromethylselenolations – synthesis of R-SeCF3compounds using air stable tetramethylammonium trifluoromethylselenate

2015 ◽  
Vol 51 (21) ◽  
pp. 4394-4397 ◽  
Author(s):  
Quentin Lefebvre ◽  
Roman Pluta ◽  
Magnus Rueping
Keyword(s):  
Oxidative Coupling ◽  
Room Temperature ◽  
Boronic Acids ◽  
Coupling Reactions ◽  
Terminal Alkynes ◽  
Boronic Esters ◽  
Oxidative Coupling Reactions

The aerobic, room-temperature coupling of tetramethylammonium trifluoromethylselenate with readily available boronic acids, boronic esters, and terminal alkynes has been developed.

Paramagnetic Intermediates in Oxidative Coupling Reactions of Tertiary Aromatic Amines in Liquid Sulphur Dioxide

1974 ◽  
Vol 29 (5-6) ◽  
pp. 403-407 ◽  
Author(s):  
M. Donbavand ◽  
H. Möckel
Keyword(s):  
Sulphur Dioxide ◽  
Oxidative Coupling ◽  
Aromatic Amines ◽  
Coupling Reactions ◽  
Oxidation Reactions ◽  
Cation Radicals ◽  
Radical Intermediates ◽  
Liquid Sulphur ◽  
Oxidative Coupling Reactions ◽  
Coupling Processes

Results are presented which complement earlier studies on oxidative coupling processes in aromatic amines and demonstrate strikingly the ease with which such reactions take place in liquid sulphur dioxide. Further, yields and stability of the intermediate cation radicals in this solvent compared with others of similar dielectric constant implies the participation of ionising forces not directly connected with dielectric properties. It is suggested that liquid SO2 may prove a very useful solvent in which to study radical intermediates of many oxidation reactions.

scholarly journals An Efficient Metal-Free Oxidative Esterification and Amination of Benzyl C–H Bond

Molecules ◽  
2020 ◽  
Vol 25 (7) ◽  
pp. 1527
Author(s):  
Saiwen Liu ◽  
Ru Chen ◽  
Guowen He ◽  
Jin Zhang
Keyword(s):  
Carboxylic Acids ◽  
Oxidative Coupling ◽  
Coupling Reactions ◽  
Coupling Reagents ◽  
Oxidative Esterification ◽  
Metal Free ◽  
High Yields ◽  
Oxidative Coupling Reactions

An esterification and amination of benzylic C–H bonds was developed by using 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) under metal- and iodide-free conditions. Both carboxylic acids and amines could be used as ideal coupling partners for the oxidative coupling reactions with various diarylmethanes. A close to equal amount of coupling reagents was enough to afford the product in good to high yields.

An Iron-Based Catalyst Enables The Enantioconvergent Synthesis of Chiral 1,1-Diarylalkanes Through a Suzuki-Miyaura Cross-Coupling Reaction

2020 ◽  
Author(s):  
Chet Tyrol ◽  
Nang Yone ◽  
Connor Gallin ◽  
Jeffery Byers
Keyword(s):  
Coupling Reaction ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Radical Intermediates ◽  
Cross Coupling Reactions ◽  
Cross Coupling Reaction ◽  
Boronic Esters ◽  
Carbon Centered Radical ◽  
Iron Based ◽  
High Yields

By using an iron-based catalyst, access to enantioenriched 1,1-diarylakanes was enabled through an enantioselective Suzuki-Miyaura crosscoupling reaction. The combination of a chiral cyanobis(oxazoline) ligand framework and 1,3,5-trimethoxybenzene additive were essential to afford high yields and enantioselectivities in cross-coupling reactions between unactivated aryl boronic esters and a variety of benzylic chlorides, including challenging ortho-substituted benzylic chloride substrates. Mechanistic investigations implicate a stereoconvergent pathway involving carbon-centered radical intermediates.

An Unprecedented Cyano-Induced Sodium Nitrite-Catalyzed C(sp3)-H and C(sp2)-H Coupling Reaction

2018 ◽  
Vol 15 (7) ◽  
pp. 989-994 ◽  
Author(s):  
Ling Li ◽  
Bo Su ◽  
Yuxiu Liu ◽  
Qingmin Wang
Keyword(s):  
Sodium Nitrite ◽  
Oxidative Coupling ◽  
High Resolution Mass Spectrometry ◽  
Coupling Reaction ◽  
13C Nmr Spectroscopy ◽  
Coupling Reactions ◽  
Reaction Conditions ◽  
1H And 13C Nmr ◽  
Oxidative Coupling Reaction ◽  
Oxidative Coupling Reactions

Aim and Objective: During the investigation of sodium nitrite-catalyzed oxidative coupling reaction of aryls, an unprecedented C(sp2)-H and C(sp3)-H coupling of substituted 2-aryl acetonitrile was found. Materials and Methods: The structure of the coupled product was confirmed by 1H and 13C NMR spectroscopy and high-resolution mass spectrometry (HRMS), and comparison of its derivatives with known compounds. The effects of methoxy group in the benzene ring on the reaction were evaluated. Results: The optimized reaction conditions are summarized as follows: CF3SO3H/substrate = 1.5 equiv., NaNO2/substrate = 0.3 equiv., CH3CN as solvent. 2-(4-Methoxyphenyl)acetonitrile and 2-(3,4,5- trimethoxyphenyl)acetonitrile could also generate C(sp2)-H and C(sp3)-H coupling. The coupling reaction occurred as a typical radial mechanism. Conclusion: An unprecedented cyano-induced, NaNO2-catalyzed oxidative C(sp3)-H and C(sp2)-H coupling was reported. The reaction proceeded under very mild conditions, using O2 in the air as terminal oxidant. The unique oxidative manner might provide more inspiration for the development of intriguing oxidative coupling reactions.

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