RT Journal Article
T1 Switching Selectivity in Borylative Allyl–Allyl Cross-Coupling through Synergistic Catalysis
A1 Vázquez-Galiñanes, Nuria
A1 Sciortino, Giuseppe
A1 Piñeiro-Suárez, Martín
A1 Tóth, Balázs L.
A1 Maseras, Feliu
A1 Fañanás-Mastral, Martín
K1 Allyl Group
K1 Inorganic Carbon Compounds
K1 Palladium
K1 Selectivity
K1 Stereoselectivity
AB A Cu/Pd-catalyzed borylative coupling of allenes with allyl carbonates is reported. Synergistic Cu/Pd catalysis enables a divergent selectivity compared to Cu catalysis and allows for the regio-, diastereo-, and enantioselective formation of synthetically versatile chiral borylated 1,5-dienes featuring two adjacent tertiary stereocenters. DFT calculations support a closed inner-sphere SE2′ transmetalation between the catalytic allyl copper and allyl palladium intermediates and point at the reductive elimination of the resulting bis(allyl)Pd intermediate as the regio- and diastereo-determining step. 
PB American Chemical Society
SN 0002-7863
YR 2024
FD 2024-07-24
LK https://hdl.handle.net/10347/39822
UL https://hdl.handle.net/10347/39822
LA eng
NO Nuria Vázquez-Galiñanes, Giuseppe Sciortino, Martín Piñeiro-Suárez, Balázs L. Tóth, Feliu Maseras, and Martín Fañanás-Mastral Journal of the American Chemical Society 2024 146 (31), 21977-21988 DOI: 10.1021/jacs.4c07188
NO Financial support from the MCIN/AEI (PID2020-118237RB-I00, PID2020-112825RB-I00, and CEX2019-000925-S), European Research Council (863914), Xunta de Galicia (ED431C 2022/27; Centro singular de investigación de Galicia accreditation 2019-2022, ED431G 2019/03), and CERCA Programme/Generalitat de Catalunya and the European Regional Development Fund (ERDF) is gratefully acknowledged. N.V.-G. and M.P.-S. thank AEI for FPI predoctoral fellowships.
DS Minerva
RD 28 abr 2026