Cross-coupling Of Anilines Research Articles

A Dual CQD-Catalysis and H-Bond Acceptor for Controlling Product Selectivity and Regioselectivity in Symmetric/Unsymmetric Azoxy Arenes.

Azoxy arenes are valuable compounds in different areas of chemistry, such as organic chemistry, medicinal chemistry, and natural product chemistry. Despite their value, the regioselective synthesis of unsymmetric azoxybenzenes has remained a real challenge in the field. Herein, the product selectivity in oxidative homocoupling of anilines into symmetric azoxybenzenes was first achieved by an asparagine-functionalized CQD catalyst. Subsequently, in the cross-coupling of anilines into the unsymmetric azoxybenzenes via an ortho H-bond acceptor (HBA) on one of the coupling anilines, the regioselectivity was effectively controlled. It was demonstrated that ortho-HBA could mechanistically establish a six-membered intramolecular hydrogen-bonded ring on an N,N'-dihydroxy intermediate. The formed hydrogen bond makes the nearby nitrogen eminently suitable for the slow dehydration step. As a result, the functional oxygen of the azoxy compound is placed far from the HBA. The o-HBA mechanism also controls the regioselectivity ratio in which 1:0 (with an intramolecular H-bonded hexagonal ring), 2:1 (with an intramolecular H-bonded pentagonal ring), and 1:1 (without an ortho-HBA) isomeric mixtures could be achieved. The HBA mechanism was exploited by different substituted anilines, and various unsymmetric azoxybenzenes were synthesized. Finally, with the aid of mechanistic studies, a plausible mechanism for the reaction was proposed.

Photoinduced Reduction of Nitroarenes and Tandem C-N Cross-Coupling with Haloarenes.

An efficient photocatalytic C-N cross-coupling of nitroarenes with haloarenes has been developed using simple and cheap Ni(acac)2 as a cocatalyst. The reaction is confirmed as a stepwise process: (1) metal free photoinduced reduction of nitroarenes into aniline derivatives and (2) photo- and Ni-catalyzed C-N cross-coupling of anilines with haloarenes. The reaction conditions are simple and mild, giving high-value diarylamines with good to excellent yields and good functional group tolerance.

Ruthenium-Catalyzed Cross-Coupling of Anilines

Ruthenium-Catalyzed Cross-Coupling of Anilines

Photocatalytic C–N Bond Activation and Cross-Coupling of Anilines

Photocatalytic C–N Bond Activation and Cross-Coupling of Anilines

ChemInform Abstract: Iodine‐Promoted Oxidative Cross‐Coupling of Unprotected Anilines with Methyl Ketones: A Site‐Selective Direct C—H Bond Functionalization to C4‐Dicarbonylation of Anilines.

An unprecedented direct dual C–H bond functionalization of unprotected anilines and methyl ketones has been demonstrated. It is the first example of iodine-promoted highly chemo- and site-selective oxidative C–H/C–H cross-coupling of anilines and methyl ketones to furnish the C4-dicarbonylation of anilines in moderate to good yields. Moreover, coproduct HI acted as a catalyst in the reaction. The salient feature of this approach is unprecedented C–H functionalization rather than N–H functionalization of unprotected anilines.

Iodine-Promoted Oxidative Cross-Coupling of Unprotected Anilines with Methyl Ketones: A Site-Selective Direct C–H Bond Functionalization to C4-Dicarbonylation of Anilines

An unprecedented direct dual C-H bond functionalization of unprotected anilines and methyl ketones has been demonstrated. It is the first example of iodine-promoted highly chemo- and site-selective oxidative C-H/C-H cross-coupling of anilines and methyl ketones to furnish the C4-dicarbonylation of anilines in moderate to good yields. Moreover, coproduct HI acted as a catalyst in the reaction. The salient feature of this approach is unprecedented C-H functionalization rather than N-H functionalization of unprotected anilines.