Dearomatization of 3‐Nitroindoles with Highly γ‐Functionalized Allenoates in Formal (3+2) Cycloadditions

Léo Birbaum (1) , Laurent Gillard (1) , Hélène Gérard (2) , Hassan Oulyadi (1) , Guillaume Vincent (3) , Xavier Moreau (4) , Michaël de Paolis (1) , Isabelle Chataigner (1, 2)

1 COBRA - Chimie Organique et Bioorganique : Réactivité et Analyse
2 LCT - Laboratoire de chimie théorique
3 ICMMO - Institut de Chimie Moléculaire et des Matériaux d'Orsay
4 ILV - Institut Lavoisier de Versailles

3‐Nitroindoles are easily reacted with highly substituted γ‐allenoates in the presence of a commercially available phosphine catalyst. For instance, allenoates derived from biomolecules such as amino and deoxycholic acids are combined for the first time with 3‐nitroindole. The corresponding dearomatized (3+2) tricyclic cycloadducts are obtained as α‐regioisomers exclusively. DFT computations shed light on this multi‐step reaction mechanism and on the selectivities observed in the sequence.

Domains: Chemical Sciences

Léo Birbaum, Laurent Gillard, Hélène Gérard, Hassan Oulyadi, Guillaume Vincent, et al.. Dearomatization of 3‐Nitroindoles with Highly γ‐Functionalized Allenoates in Formal (3+2) Cycloadditions. Chemistry - A European Journal, 2019, 25 (60), pp.13688-13693. ⟨10.1002/chem.201903455⟩. ⟨hal-02330833⟩