Lanthanide‐mediated Defluorinative Transformations of Trifluoromethylated Benzofulvenes: Access to Functionalized Difluoroalkenes and Mechanistic Insights
Accessing difluorinated organic molecules via selective C-F bond activation in CF<sub>3</sub>-containing substrates has become a valuable synthetic pathway. The combination of lanthanide metals (lanthanum, dysprosium) with Lewis acids (AlCl<sub>3</sub>, LaI<sub>3</sub>) allows the efficient regio- and stereoselective transformation of CF<sub>3</sub>-benzofulvenes into a range of versatile difluoroalkenes proceeding via ϵ,ϵ-difluoropentadienyl lanthanide or aluminium species. The reaction of these organometallic intermediates towards ketones and nitroalkenes is herein reported and analyzed in relation to previous studies on aldehydes. The influence of steric and electronic factors of the organic substrates but also of the lanthanide metals and Lewis acids on the regio and stereoselective reaction is highlighted and corroborated by in-depth DFT studies. The resulting difluorinated homoallylic alcohols and nitroalkanes were further functionalized to new benzofulvenes and their reactivity explored.
Authors
- Deepak Mali
- Yan Yang (ORCID: https://orcid.org/0000-0003-3808-269X)
- Poonam Khandelwal (ORCID: https://orcid.org/0000-0003-2443-4041)
- Maxime Bouquin
- Jean‐Bernard Behr (ORCID: https://orcid.org/0000-0002-8998-8806)
- Florian Jaroschik (ORCID: https://orcid.org/0000-0003-0201-568X)
- Marc Taillefer (ORCID: https://orcid.org/0000-0003-2991-5418)
- Amira Ben Hassine (ORCID: https://orcid.org/0000-0002-4641-0617)
- Fabien Massicot (ORCID: https://orcid.org/0000-0002-1400-6804)
- Laurent Maron (ORCID: https://orcid.org/0000-0003-2653-8557)
- Tarun Kumar (ORCID: https://orcid.org/0000-0002-3210-0036)
- Sylviane Chevreux
- Yogita Prajapat
Institutions
- École Nationale Supérieure de Chimie de Montpellier (FR)
- Centre National de la Recherche Scientifique (FR)
- Université Toulouse III - Paul Sabatier (FR)
- Université Fédérale de Toulouse Midi-Pyrénées (FR)
- Institut National des Sciences Appliquées de Toulouse (FR)
- Université de Montpellier (FR)
- Université Paris Sciences et Lettres (FR)
- Institut Charles Gerhardt Montpellier (FR)
- Institut de Recherche de Chimie Paris (FR)
- Institut de Chimie Moléculaire de Reims (FR)
- Laboratoire de Physique et Chimie des Nano-Objets (FR)
- Mohanlal Sukhadia University (IN)
- Université de Reims Champagne-Ardenne (FR)
Publication Details
- Journal
- Chemistry - An Asian Journal
- Published
- 2025-03-13
- DOI
- https://doi.org/10.1002/asia.202500071
- Primary Topic
- Fluorine in Organic Chemistry
- Type
- article
- Field-Weighted Citation Impact
- 0.00