Base-Assisted Intramolecular C–N Coupling Reaction from NH 2 -Bound Cyclopalladated L -Phenylalanine to Indoline-2-carboxylic Acid

Aurélien Jacquin-Labarre (1) , Sébastien Coufourier (1) , Rodolphe Tamion (2) , Alexandra Le Foll (1) , Vincent Levacher (1) , Carlos Afonso (1) , Vincent Gandon (3) , Guillaume Journot (2) , Jean-François Brière (1) , Christophe Hoarau (1)

1 COBRA - Chimie Organique et Bioorganique : Réactivité et Analyse
2 Oril Industrie
3 ICMMO - Institut de Chimie Moléculaire et des Matériaux d'Orsay

The deprotonative intramolecular-amination reaction of phenylalanine-derived palladacycles has been investigated to highlight a facile carbonate-assisted N–H activation before the C–N bond formation. A major counterion effect led to divergent pathways whereby the SPhos-Pd complexes with iodine, triflate, or trifluoroacetate anions were key intermediates to afford access to (S)-2-indolinecarboxylic acid derivatives.

Keywords: Aromatic compounds; Organic reactions; Palladium; Mixtures; Indoles

Domains: Chemical Sciences; Catalysis; Chemical Sciences; Organic chemistry

Aurélien Jacquin-Labarre, Sébastien Coufourier, Rodolphe Tamion, Alexandra Le Foll, Vincent Levacher, et al.. Base-Assisted Intramolecular C–N Coupling Reaction from NH 2 -Bound Cyclopalladated L -Phenylalanine to Indoline-2-carboxylic Acid. Organometallics, 2020, 39 (5), pp.767-773. ⟨10.1021/acs.organomet.0c00030⟩. ⟨hal-02493098⟩