Passerini-Smiles Reaction of α-Ketophosphonates: Platform for Phospha-Brook/Smiles Embedded Cascades.
- Resource Type
- Academic Journal
- Authors
- Cheibas C; Laboratoire de Synthèse Organique (LSO-UMR 76523), CNRS, Ecole Polytechnique, ENSTA-Paris, Institut Polytechnique de Paris, 828 Bd des Maréchaux, 91128, Palaiseau Cedex, France.; Fincias N; Laboratoire de Synthèse Organique (LSO-UMR 76523), CNRS, Ecole Polytechnique, ENSTA-Paris, Institut Polytechnique de Paris, 828 Bd des Maréchaux, 91128, Palaiseau Cedex, France.; Casaretto N; Laboratoire de Chimie Moléculaire (LCM-UMR 9168), CNRS, Ecole Polytechnique, Institut Polytechnique de Paris, 91128, Palaiseau Cedex, France.; Garrec J; Unité Chimie et Procédés (UCP), ENSTA-Paris, Institut Polytechnique de Paris, 91128, Palaiseau Cedex, France.; El Kaïm L; Laboratoire de Synthèse Organique (LSO-UMR 76523), CNRS, Ecole Polytechnique, ENSTA-Paris, Institut Polytechnique de Paris, 828 Bd des Maréchaux, 91128, Palaiseau Cedex, France.
- Source
- Publisher: Wiley-VCH Country of Publication: Germany NLM ID: 0370543 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1521-3773 (Electronic) Linking ISSN: 14337851 NLM ISO Abbreviation: Angew Chem Int Ed Engl Subsets: PubMed not MEDLINE; MEDLINE
- Subject
- Language
- English
The Passerini-Smiles reactions of α-ketophosphonates with nitrophenols has been used as a platform to observe complex cascades involving multiple Smiles transfers coupled with phospha-Brook rearrangement. When using 4-nitrophenols a rare 1,3-Truce-Smiles rearrangement is observed leading to diarylacetamide derivatives. 2-Nitro-derivatives lead to a completely different reactivity pattern that may be explained by a nitro to nitroso conversion followed by a σ-π metathesis. All mechanistic assumptions are confirmed by DFT calculations performed on both families of adducts. The potential of this work has been further demonstrated by the use of N-aryl α-ketoamides as alternative starting materials for these cascades as well as the disclosure of new aza-Nazarov access to hydroxy-indolones.
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