A Copper‐Catalyzed Decarboxylative Amination/Hydroamination Sequence: Switchable Synthesis of Functionalized Indoles

Abstract

A copper-catalyzed decarboxylative amination/hydroamination sequence of propargylic carbamates with various nucleophiles is described for the first time. It features an earth-abundant metal catalyst, mild reaction conditions, and high efficiency. Further treatments of the resultant key intermediates using an acid or a base in one pot enable the controllable and divergent synthesis of two types of functionalized indoles. Moreover, experiments to demonstrate the synthetic potential of this methodology are performed.

Catalytic Oxidative Coupling Cyclization for Construction of Benzofuroindolenines under Mild Reaction Conditions

“…[1] Diverse elegant methods extensively complemented the fields of traditional coupling reactions and provided widely applicable approaches for new bond formation. [2] Efficient oxidative coupling protocols for functionalized indoles have been developed by the groups of Harran, [3] Danishefsky, [4] Trost, [5] Nicolaou, [6] Overman, [7] Muniz, [8] MacMillan, [9] Xiao, [10] Lei, [11] Vincent, [12] You, [13] Stephenson, [14] and others. [15] While, the synthetic utility of catalytic oxidative coupling cyclization for construction of complex benzofuroindolenines has not been fully developed.…”

Manganese(I)‐Catalyzed C−H (2‐Indolyl)methylation: Expedient Access to Diheteroarylmethanes

“…[8] This complex is an electrophilic center and can react with nucleophiles to achieve propargylation and further annulation. [8] This complex is an electrophilic center and can react with nucleophiles to achieve propargylation and further annulation.…”

“…Recently,t he Xiao group and others have demonstrated that ethynyl benzoxazinanones and their analogues can easily interact with late-transition metals such as Cu to furnish versatile metal-allenylidene intermediates (Scheme 2, path a). [8] This complex is an electrophilic center and can react with nucleophiles to achieve propargylation and further annulation. Fort he metal-allenylidene intermediates to be involved in catalytic processes,t he metal moiety must be chosen to allow ag ood compromise between ligand electrophilicity and metal-ligand bond stability.…”

Mangan(I)‐katalysierte C‐H‐(2‐Indolyl)methylierung: ein einfacher Zugang zu Diheteroarylmethan‐Derivaten

“…[8] Dieser Komplex ist ein elektrophiles Zentrum und kann mit Nucleophilen reagieren und Propargylierung sowie weitere Anellierung ermçglichen. [8] Dieser Komplex ist ein elektrophiles Zentrum und kann mit Nucleophilen reagieren und Propargylierung sowie weitere Anellierung ermçglichen.…”

“…Kürzlich haben die Gruppe von Xiao und andere gezeigt, dass Ethinylbenzoxazinanon und dessen Analoga leicht mit späten Übergangsmetallen wie Cu wechselwirken kçnnen, was vielseitige Metall-Allenyliden-Intermediate liefert (Schema 2, Pfad a). [8] Dieser Komplex ist ein elektrophiles Zentrum und kann mit Nucleophilen reagieren und Propargylierung sowie weitere Anellierung ermçglichen. Um Metall-Allenyliden-Intermediate in katalytische Prozesse einzubinden, muss das Metall so gewählt werden, dass ein guter Kompromiss zwischen Ligandenelektrophilie und Metall-Ligand-Bindungsstabilitätm çglich ist.…”