Year: 2025
Type: article
Abstract: Difluorocarbene is a very powerful synthon in organic chemistry, but its reactivity is very challenging to tame. While a few recent studies have pinpointed the potential of transition metals such as Pd and Cu to stabilize and harness difluorocarbene, known examples are confined to relatively classical transformations. Here we report gold(I) difluorocarbenes persisting for hours at 0 °C thanks to ligand-enhanced backdonation. These complexes exhibit unforeseen reactivity with alkenes and 1,3-dienes. The key intermediates, gold(III) metallacycles, have been spectroscopically and crystallographically characterized. Choosing the ligand at gold and operating conditions (thermal or photochemical) enable to direct C─C coupling to the desired product. This novel gold-mediated two-electron redox pathway was leveraged to prepare difluorocyclopentenes, overcoming the intrinsic challenge of [1+4] cycloaddition between carbenes and 1,3-dienes.
Institutions: Centre National de la Recherche Scientifique, Laboratoire Hétérochimie Fondamentale et Appliquée, Université de Toulouse, Université de Pau et des Pays de l'Adour, Institut des Sciences Analytiques et de Physico-Chimie pour l'Environnement et les Matériaux, Institut de Chimie de Toulouse
Language: English
Subfield: Pharmaceutical Science
Domain: Life Sciences
Open Access status: hybrid
Estimated APC paid: $5,510
OpenAlex ID: W4414337590