How electrophilic are 3-nitroindoles? Mechanistic investigations and application to a reagentless (4+2) cycloaddition

Batoul Rkein (1) , Maxime Manneveau (1) , Ludovik Noël-Duchesneau (2) , Karine Pasturaud (1) , Muriel Durandetti (1) , Julien Legros (1) , Sami Lakhdar (2, 3) , Isabelle Chataigner (1, 4)

1 COBRA - Chimie Organique et Bioorganique : Réactivité et Analyse
2 LCMT - Laboratoire de chimie moléculaire et thioorganique
3 LHFA - Laboratoire Hétérochimie Fondamentale et Appliquée
4 LCT - Laboratoire de chimie théorique

The electrophilicity of 4 different 3-nitroindole derivatives has been evaluated by Mayr’s linear free energy relationship (log k(20 °C) = sN(E + N)) and reveals unexpected values for aromatic compounds, in the nitrostyrene range. 3-Nitroindoles are sufficiently electrophilic to interact with a common diene namely the Danishefsky's diene at room temperature, in the absence of any activator, to furnish smoothly the dearomatized (4+2) cycloadducts in good yields.

Domaines: Chimie organique

Batoul Rkein, Maxime Manneveau, Ludovik Noël-Duchesneau, Karine Pasturaud, Muriel Durandetti, et al.. How electrophilic are 3-nitroindoles? Mechanistic investigations and application to a reagentless (4+2) cycloaddition. Chemical Communications, 2021, pp.10071-10074. ⟨10.1039/D1CC04074J⟩. ⟨hal-03353835⟩