Details

Autor(en) / Beteiligte

• Yu, Huimin
• Zhang, Qinglong
• Zi, Weiwei

Titel

Synergistic Pd/Cu-catalyzed enantioselective Csp2–F bond alkylation of fluoro-1,3-dienes with aldimine esters

Ist Teil von

• Nature communications, 2022-05, Vol.13 (1), p.2470-2470, Article 2470

Ort / Verlag

London: Nature Publishing Group

Erscheinungsjahr

2022

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• Abstract Due to high bond dissociation energies of Csp 2 –F bonds, using fluorinated compounds in Csp 2 –Csp 3 cross-coupling is difficult. Here the authors report a protocol for enantioselective Csp 2 –Csp 3 coupling of dienyl fluorides with aldimine esters, enabled by synergistic copper and palladium catalysis. This reaction represents the first example of asymmetric Csp 2 –Csp 3 cross-coupling involving an inert Csp 2 –F bond and provides expeditious access to chiral α-alkenyl α-amino acids with high enantioselectivity. Control experiments suggest that the Csp 2 –F bond activation occurs through a pathway involving PdH migratory insertion and subsequent allylic defluorination, rather than by direct oxidative addition of the Csp 2 –F bond to Pd(0). The detailed mechanism is further investigated by DFT calculation and the enantioselectivity is rationalized.