Intramolecular Oxidative Palladium-Catalyzed Amination Involving Double C–H Functionalization of Unactivated Olefins

Abstract

Intramolecular palladium-catalyzed amination reactions are becoming important tools for the synthesis of various nitrogen-containing­ heterocycles. This account highlights the developments achieved in this field by domino processes in oxidative conditions using unactivated olefins, due to their advantages in terms of step economy and efficiency. These reactions involve the change of oxidation state in the palladium intermediate, requiring the presence of an oxidizing agent to regenerate the catalytic cycle. This kind of additive is essential for the success of the reaction and it can also furnish nucleophilic species that are incorporated into the final product. Reactions can occur at either the intra/intra- or intra/intermolecular level, providing valuable methodologies for the preparation of (poly)heterocyclic scaffolds. Besides, procedures based on the use of strengthened catalytic systems, more recently, disclosed intriguing conditions have enlarged the possibility to modulate the substrate reactivity. Perspectives in this field are directed to the discovery of new reaction conditions, focusing on the employment of oxidatively stable ligands useful for the asymmetric catalysis­.1 Introduction2 Carboamination Reactions2.1 Pd(0)/Pd(II)2.2 Pd(II)/Pd(IV)3 Aminooxygenation Reactions3.1 Pd(0)/Pd(II)3.2 Pd(II)/Pd(IV)4 Diamination Reactions4.1 Pd(0)/Pd(II)4.2 Pd(II)/Pd(IV)5 Aminohalogenation Reactions5.1 Pd(0)/Pd(II)5.2 Pd(II)/Pd(IV)6 Conclusions

Switchable Oxidative Reactions of N-allyl-2-Aminophenols: Palladium-Catalyzed Alkoxyacyloxylation vs an Intramolecular Diels–Alder Reaction

“…The construction of functionalized heteropolycyclic molecules in one step, with the advantage to avoid isolation of intermediates is an attractive goal compared to traditional stepwise synthesis. 1 Moreover, the formation of several bonds combined in one pot complies with the concept of green chemistry in terms of timesaving and due to the reduced waste production. 2 The interest of a domino processes may be increased by using transition metal catalysis; 3 in particular, the use of palladium(II) catalyst in oxidative conditions offers the possibility to use unactivated substrates as the unsaturated systems.…”

Iodoamination of Alkenyl Sulfonamides by Potassium Iodide and Hydrogen Peroxide in Aqueous Medium

“…The oxazolidin-2-one ring is slightly distorted toward a half-chair conformation. Unit cell (Å, deg, Å 3 X-Ray quality crystals (prismatic habit, colorless) were grown by slow evaporation (ca. 6 h) from a 1 : 1 hexane/CH 2 Cl 2 mixture at room temperature.…”

“…Recently, haloamination of C=C double bond involving an intramolecular carbonÀ nitrogen bond formation received great attention as fruitful methodology for the synthesis of nitrogen-containing heterocycles. [1][2][3] The usefulness of heterocycles containing a vicinal haloamine moiety as versatile synthetic intermediates [4][5][6][7] or as potential medicinal agents [8,9] is well established.…”

Transition Metal‐Catalyzed Carboamination of Alkenes and Allenes: Recent Progress

“…In this context, carboamination of alkenes and allenes has provided a straightforward route for the synthesis of functionalized amines and their congener heterocycles. [1][2][3][4][5][6][7][8][9][10][11][12] Initial efforts on carboamination of alkenes and allenes were directed towards the aza-Diels-Alder reaction and the developed strategies were also applied in the total synthesis of natural products like (À )-mappicine and (+)-camptothecin. [10][11][12][13] The carboamination processes, broadly can be envisaged in two path-ways i. e. radical path-way and ionic path-way (Scheme 1).…”