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Dearomatization of 3-Nitroindoles with Highly γ-Functionalized Allenoates in Formal (3+2) Cycloadditions |
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| Authors: | Léo Birbaum Dr Laurent Gillard Prof Hélène Gérard Prof Hassan Oulyadi Dr Guillaume Vincent Prof Xavier Moreau Dr Michael De Paolis Prof Isabelle Chataigner |
| Institution: | 1. UNIROUEN, INSA Rouen, CNRS, COBRA, Normandie Univ, 76000 Rouen, France;2. CNRS, Laboratoire de Chimie Théorique, LCT UMR7616, Sorbonne Université, 75005 Paris, France;3. Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Univ. Paris-Sud, Université Paris-Saclay, CNRS UMR 8182, 91405 Orsay cedex, France;4. Institut Lavoisier Versailles, UMR CNRS 8180, Université de Versailles-St-Quentin-en-Yvelines, Université Paris Saclay, 78035 Versailles cedex, France |
| Abstract: | 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. |
| Keywords: | annulation allenoate dearomatization density functional calculation nitrondole |