Palladium/Copper‐Catalyzed Oxidative CH Alkenylation/N‐Dealkylative Carbonylation of Tertiary Anilines

Abstract

C‐H/C‐N‐Aktivierung: Die erste Palladium/Kupfer‐katalysierte aerobe oxidative C‐H‐Alkenylierung/N‐desalkylierende Carbonylierung von tertiären Anilinen wurde entwickelt. Die Reaktion ist mit vielen funktionellen Gruppen kompatibel, kann auch Acrylester umsetzen und ermöglichte die effiziente Synthese von biologisch aktiven 3‐Methylenindolin‐2‐onen aus preiswerten und einfachen Substraten.

Eco‐Efficient Synthesis of New Pyrido [2, 3‐c] Coumarin Scaffolds Under Sonochemical Method

“…Hantzsch DHP synthesis is one of the most broadly used methods for the preparation of DHPs. In order to improve the efficiency of Hantzsch DHPs synthesis, different catalysts have been explored, and many of them exhibited excellent catalytic activity [16][17][18][19], such as L-proline [20], S-Valin [21], Yb(OTf) 3 [22], molecular I 2 [23], TBAHS [24], HOAc [25], Et 3 N [26], DBU [27], Py [28], ceric ammonium nitrate (CAN) [29], and so on. These methods, however, suffer from drawbacks such as the use of expensive catalysts, difficulty in availability or preparing the starting materials or catalysts, the environmental pollution caused by utilization of solvents and homogeneous catalysts, low yields, long reaction times, tedious work-up, waste control, and formation of side products.…”

Room‐Temperature Palladium‐Catalyzed Intramolecular Oxidative Aminocarbonylation of Vinylic C(sp2)–H Bonds with Amines and CO

“…The nitrogen atom in substrate 1 can readily complex with the PdL 2 Y 2 species to afford intermediate A 6,7. Subsequently, two of the following pathways may take place: (i) sequential reactions of the amine with CO and the insertion of the PdL 2 Y 2 species into the vinyl C–H bond of intermediate A to give Pd III intermediate D 7 or ii) sequential reactions of the amine with CO and an oxidative Heck reaction to form intermediate E 6c. Finally, the reductive elimination of either intermediate D or E affords both product 2 and the Pd 0 L n species.…”

N‐Oxide as a Traceless Oxidizing Directing Group: Mild Rhodium(III)‐Catalyzed CH Olefination for the Synthesis of ortho‐Alkenylated Tertiary Anilines

“…5 In addition, the N , N ‐dimethylaminomethyl group has been disclosed as a directing group for both oxidative Heck and arylation reactions 6. However, the transition‐metal‐catalyzed CH activation of tertiary anilines remains less developed except for few examples on para ‐selective transformations7 and the recently reported oxidative ortho CH alkenylation/N‐dealkylative carbonylation of tertiary anilines (tertiary amines probably act as a directing group) 8. Therefore, it is highly valuable to develop CH activation for the synthesis of ortho ‐functionalized tertiary anilines.…”