RT info:eu-repo/semantics/article
T1 Understanding the Use of Phosphine-(EWO) Ligands in Negishi Cross-Coupling: Experimental and Density Functional Theory Mechanistic Study
A1 Gioria, Estefanía
A1 Pozo, Juan del
A1 Lledós, Agustí
A1 Espinet Rubio, Pablo
K1 Palladium
K1 Paladio
K1 Transmetalation
K1 Transmetalación
K1 Ligands
K1 Ligandos
K1 Coupling reactions
K1 Reacciones de acoplamiento
AB The easily prepared hemilabile ligand 1-(PPh2),2-(trans-CH═CHCOPh)–C6F4 (PhPEWO-F) and other PEWO ligands are well-known promoters of C–C reductive eliminations and very effective in Negishi couplings. As an example, the efficient Negishi coupling of (C6F5)–I and Zn(C6F5)2 is reported. The thorough experimental study of the steps involved in the catalytic cycle uncovers the potential weakness of this ligand that could frustrate at some points the desired cycle and provide some simple precautions to keep the catalytic cycle working efficiently. Density functional theory (DFT) calculations complete the experimental study and provide insight into nonobservable transition states and intermediates, comparing the potential conflict between reductive elimination and olefin insertion. Our results showcase the importance the transmetalation step, facilitated by the strong trans effect of the electron-withdrawing ligand, and the choice of organozinc nucleophiles, critical to ensure fast group exchange and a positive outcome of the catalytic reactions.
PB ACS Publications
SN 0276-7333
YR 2021
FD 2021
LK https://uvadoc.uva.es/handle/10324/49783
UL https://uvadoc.uva.es/handle/10324/49783
LA eng
NO Organometallics, 2021, vol. 40, n. 14. p. 2272–2282
NO Producción Científica
DS UVaDOC
RD 19-abr-2024