A symbiotic experimental/computational study analyzed the Ru(TPP)(NAr)2-catalyzed one-pot formation of indoles from alkynes and aryl azides. Thirty different C3-substituted indoles were synthesized and the best performance, in term of yields and regioselectivities, was observed when reacting ArC≡CH alkynes with 3,5-(EWG)2C6H3N3 azides, whereas the reaction was less efficient when using electron-rich aryl azides. A DFT analysis describes the reaction mechanism in terms of the energy costs and orbital/electronic evolutions; the limited reactivity of electron-rich azides was also justified. In summary, PhC≡CH alkyne interacts with one NAr imido ligand of Ru(TPP)(NAr)2 to give a residually dangling C(Ph) group, which, by coupling with a C(H) unit of the N-aryl substituent, forms a 5+6 bicyclic molecule. In the process, two subsequent spin changes allow inverting the conformation of the sp2 C(Ph) atom and its consequent electrophilic-like attack to the aromatic ring. The bicycle isomerizes to indole via a two-step outer sphere H-migration. Eventually, a ′Ru(TPP)(NAr)′ mono-imido active catalyst is reformed after each azide/alkyne reaction.

Indoles from Alkynes and Aryl Azides: Scope and Theoretical Assessment of Ruthenium Porphyrin-Catalyzed Reactions

Zardi P.
Investigation
;
Damiano C.;
2019

Abstract

A symbiotic experimental/computational study analyzed the Ru(TPP)(NAr)2-catalyzed one-pot formation of indoles from alkynes and aryl azides. Thirty different C3-substituted indoles were synthesized and the best performance, in term of yields and regioselectivities, was observed when reacting ArC≡CH alkynes with 3,5-(EWG)2C6H3N3 azides, whereas the reaction was less efficient when using electron-rich aryl azides. A DFT analysis describes the reaction mechanism in terms of the energy costs and orbital/electronic evolutions; the limited reactivity of electron-rich azides was also justified. In summary, PhC≡CH alkyne interacts with one NAr imido ligand of Ru(TPP)(NAr)2 to give a residually dangling C(Ph) group, which, by coupling with a C(H) unit of the N-aryl substituent, forms a 5+6 bicyclic molecule. In the process, two subsequent spin changes allow inverting the conformation of the sp2 C(Ph) atom and its consequent electrophilic-like attack to the aromatic ring. The bicycle isomerizes to indole via a two-step outer sphere H-migration. Eventually, a ′Ru(TPP)(NAr)′ mono-imido active catalyst is reformed after each azide/alkyne reaction.
File in questo prodotto:
Non ci sono file associati a questo prodotto.
Pubblicazioni consigliate

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11577/3343518
Citazioni
  • ???jsp.display-item.citation.pmc??? 0
  • Scopus 7
  • ???jsp.display-item.citation.isi??? 8
social impact