RESUMEN
Singlet carbenes are not always isolable and often even elude direct detection. When they escape observation, their formation can sometimes be evidenced by in situ trapping experiments. However, is carbene-like reactivity genuine evidence of carbene formation? Herein, using the first example of a spectroscopically characterized cyclic (amino)(aryl)carbene (CAArC), we cast doubt on the most common carbene trapping reactions as sufficient proof of carbene formation.
RESUMEN
The synthesis of ruthenium-complexes with cyclic (amino)(barrelene)carbenes (namely CABCs) as ligands is reported. Isolated in moderate to good yields, these new complexes showed impressive thermal stability at 110 °C over several days. Good catalytic performances were demonstrated in various ring-closing metathesis (RCM), macrocyclic-RCM, ring-closing enyne metathesis (RCEYM), cross-metathesis (CM), and ring-opening cross metathesis (ROCM) reactions.
RESUMEN
An air-stable (amino)(amido)radical was synthesized by reacting a cyclic (alkyl)(amino)carbene with carbazoyl chloride, followed by one-electron reduction. We show that an adjacent radical center weakens the amide bond. It enables the amino group to act as a strong acceptor under steric contraint, thus enhancing the stabilizing capto-dative effect.
Asunto(s)
Amidas , Lagartos , Animales , Oxidación-Reducción , Cloruros , ElectronesRESUMEN
A novel family of cyclic (alkyl)(amino)carbenes, which we name cyclic (amino)(barrelene)carbenes (CABCs) is reported. The key synthetic step involves an intramolecular [4+2] cyclization of an anthracene derivative with an alkyne. This synthetic approach allows for the attachment of both aryl and alkyl groups on the nitrogen atom. When used as ligand, two of the barrelene hydrogens are in close contact with the metal, which could stabilize low valent catalytic intermediates.
