Copper-Catalyzed Oxidative Cross-Coupling Research Articles

Formation of the Tertiary Sulfonamide C(sp3)-N Bond Using Alkyl Boronic Ester via Intramolecular and Intermolecular Copper-Catalyzed Oxidative Cross-Coupling.

A synthetic strategy for the formation of C(sp3)-N bonds, particularly through a copper-catalyzed oxidative cross-coupling, is rare. Herein, we report a novel synthetic approach for the preparation of tertiary sulfonamides via copper-catalyzed intra- and intermolecular oxidative C(sp3)-N cross-coupling reactions. This method allows the utilization of the readily available C(sp3)-based pinacol boronate as a substrate and the tolerance of a wide range of functional groups under mild reaction conditions. The success of this strategy relies on the unprecedented additive effects of silanol and NaIO4.

Synthesis of 2-oxo-acetamidines via copper-catalyzed oxidative cross-coupling of α-amino ketone compounds with amines

A general and efficient method for the synthesis of 2-oxo-acetamidines via copper-catalyzed oxidative cross-coupling of amines with α-amino ketone compounds was achieved. In this reaction, the C − N bond of α-amino ketone is broken and new C − N and CN bonds are constructed in one single transformation. This reaction system has a broad substrate scope and provides a facile pathway for the synthesis of 2-oxo-acetamidines.

Copper-Catalyzed Oxidative Cross-Coupling Reactions for the Synthesis of β-Acyl-α-amino Acid Derivatives in Aqueous Medium

Copper-Catalyzed Oxidative Cross-Coupling Reactions for the Synthesis of <i>β</i>-Acyl-<i>α-</i>amino Acid Derivatives in Aqueous Medium

Investigations of the Copper-Catalyzed Oxidative Cross-Coupling of Tetrahydroisoquinolines with Diethylzinc by a Combination of Mass Spectrometric and Electrochemical Methods.

The aerobic oxidative cross-coupling of tetrahydroisoquinolines (THIQs) with diethylzinc catalyzed by CuCl2 has been examined by means of electrospray mass spectrometry (ESI-MS). Substrates, intermediates, and the product were readily detected. Particular emphasis has been placed on the role of CuCl2 . Formation of the intermediate iminium species has been investigated in more detail by ESI-MS, electrochemistry-coupled ESI mass spectrometry (EC-MS), and cyclic voltammetry (CV). Our experiments have consistently revealed strong influences of the N-substituent of the THIQ derivative and its oxidation stability with respect to CuCl2 . The results may help to expand the synthetic scope of the reaction, while also further establishing EC-MS as a valuable technique for linking mass spectrometry with cyclic voltammetry in mechanistic studies of organic redox reactions.

Copper-catalyzed decarboxylative and oxidative decarbonylative cross-coupling between cinnamic acids and aliphatic aldehydes

A convenient copper-catalyzed decarboxylative and oxidative decarbonylative cross-coupling of cinnamic acids with aliphatic aldehydes was achieved, which provides a useful strategy of C(sp3)–C(sp2) bonds construction for the synthesis of alkyl-substituted E-alkenes.

Copper-catalyzed oxidative cross-coupling of α-aminocarbonyl compounds with primary amines toward 2-oxo-acetamidines.

A general and mild method for the construction of a carbon-nitrogen bond via copper-catalyzed oxidative cross-coupling of amines with α-aminocarbonyl compounds was achieved. Amines, either aliphatic primary amines, aromatic primary amines or secondary amines can be used as the starting materials. When R2 was different from R3, two isomers would be observed. Therefore, this reaction system has a broad substrate scope and provides a facile pathway for the synthesis of 2-oxo-acetamidines.

New Design of a Disulfurating Reagent: Facile and Straightforward Pathway to Unsymmetrical Disulfanes by Copper-Catalyzed Oxidative Cross-Coupling.

A novel reagent, which introduces two sulfur atoms in one step, was designed and used for the construction of diverse disulfanes by copper-catalyzed oxidative cross-coupling under mild reaction conditions. By applying this stable and readily prepared reagent, late-stage modification of pharmaceuticals and natural products can be achieved straightforward. The scaled-up experiments further indicated the practicality of this protocol. The pH value of the system plays a key role in achieving highly selective cleavage of the C-S bond instead of a S-S bond in the transformation.

Copper-Catalyzed Carbamoylation of Terminal Alkynes with Formamides via Cross-Dehydrogenative Coupling

An efficient approach for direct carbamoylation of terminal alkynes with formamides affording propiolamides has been developed by copper-catalyzed oxidative cross coupling of C(sp)-H and C(sp2)-H bonds in the presence of a pincer ligand with two imidazolyl groups. The catalytic reaction is compatible with diverse functional groups but sensitive to the electronic effect of terminal alkyne and the steric effect of formamides. KIE study indicates the cleavage of the carbamoyl C–H bond affording formamide radical is the rate-determining step.

Recent Advances in Copper-Catalyzed Oxidative Cross-Coupling Chemistry

Development of cross-coupling chemistry by direct functionalization of C–H or heteroatom–H bonds under oxidative conditions has recently emerged as powerful and ideal methods for the formation of carbon-carbon and carbon-heteroatom bonds. Several transition metal catalysts were successfully utilized for these kinds of transformations over the past several years. Among them, copper salts are of special importance because of their easy availability, bio-compatibility and economical advantages. This review summarizes recent advances over the past 3 years in copper-catalyzed inter- and intramolecular reactions involving C–H and X–H (X= carbon or heteroatom) under oxidative dehydrogenation process in achieving C–C, C–O, C–N, C–S and C–P bond formations. Keywords: Cross dehydrogenation, oxidative coupling, copper catalyst, C-H activation.

Copper-Catalyzed Oxidative Cross-Coupling of Tetrahydroisoquinolines

Copper-Catalyzed Oxidative Cross-Coupling of Tetrahydroisoquinolines

Copper-Catalyzed Oxidative Cross-Coupling of Boronic Acids and Masked Sulfides

Copper-Catalyzed Oxidative Cross-Coupling of Boronic Acids and Masked Sulfides

Copper-Catalyzed Oxidative Cross-Coupling of H-Phosphine Oxides with Alkenes in the Synthesis of Alkenylphosphine Oxides

The first copper-catalyzed alkene oxidative cross-coupling reaction with various R₂P(O)H compounds has been reported, affording a novel and efficient method for the synthesis of valuable alkenylphosphine oxides compounds with broad substrate applicability and succinct reaction system with immoderate to good yields.

Ligand-Assisted Copper-Catalyzed Oxidative Cross-Coupling of Simple Phenols with Formamides for the Synthesis of Carbamates

An oxidative approach for the synthesis of phenyl carbamates has been achieved by ligand-assisted copper-catalyzed cross-dehydrogenative coupling (CDC) of phenols with formamides. The direct coupling of simple phenols with mono- and dialkyl form­amides provides carbamate products in moderate to good yields ­under mild reaction conditions.

Copper-catalyzed aerobic oxidative cross-coupling of arylamines and dialkylphosphites leading to N-arylphosphoramidates

An efficient method to generate N–P bonds directly from N–H and P–H bonds is described. Various arylamines and dialkylphosphites were directly oxidized to the corresponding N-arylphosphoramidates at room temperature in moderate to good yields by using an inexpensive catalyst–oxidant (CuBr/air) system.

Copper-Catalyzed Oxidative Cross-Coupling of Sulfoximines and Alkynes

Copper-Catalyzed Oxidative Cross-Coupling of Sulfoximines and Alkynes

Synthesis of Aryl Thiocyanates via Copper-Catalyzed Aerobic Oxidative Cross-Coupling between Arylboronic Acids and KSCN

A new protocol for the preparation of aryl thiocyanates by the cross-coupling reaction of arylboronic acids with KSCN salt is described. The coupling reaction was catalyzed by 20 mol% of copper acetate in the presence of 2.0 equivalents 4-methylpyridine serving both as ligand and base under 0.2 MPa of molecular oxygen. A variety of arylboronic acids, including those with substituents at <i>ortho</i> position, were suitable under the reaction conditions.

Copper‐Catalyzed Oxidative Cross‐Coupling of Sulfoximines and Alkynes

Ein präparativ nützliches Protokoll für die Synthese von N-alkinylierten Sulfoximinen (Insulfoximine) wurde entwickelt. Die Methode umfasst eine milde Kupfer-katalysierte oxidative Kreuzkupplung von NH-Sulfoximinen mit terminalen Alkinen (siehe Schema). Säurekatalysierte Hydrolyse der Insulfoximine führte selektiv zu den entsprechenden N-Acylsulfoximinen.

Copper-Catalyzed Oxidative Cross-Coupling of H-Phosphonates and Amides to N-Acylphosphoramidates

A simple combination of copper(II) acetate (Cu(OAc)(2)) and an appropriate base could promote oxidative cross-coupling of H-phosphonates and amides using air as a terminal oxidant. The substrate scope was broad with respect to both dialkyl H-phosphonates and nitrogen nucleophiles (including oxazolidinone, lactam, pyrrolidinone, urea, indole, and sulfonamide derivatives), giving the corresponding P-N coupling products in moderate to high yields.

Copper-Catalyzed Oxidative Trifluoromethylation of Boronic Acids

A copper-catalyzed oxidative cross-coupling of readily available aryl- and alkenylboronic acids with (trifluoromethyl)trimethyl­silane is reported. The reaction proceeds under mild conditions and tolerates a wide range of functional groups. Thus, the introduction of tri­fluoromethyl groups in advanced and highly ­functionalized compounds can be achieved at a late synthetic step.