Switching Selectivity in Borylative Allyl-Allyl Cross-Coupling through Synergistic Catalysis.
J Am Chem Soc
; 146(31): 21977-21988, 2024 Aug 07.
Article
in En
| MEDLINE
| ID: mdl-39046799
ABSTRACT
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.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
J Am Chem Soc
Year:
2024
Document type:
Article
Affiliation country:
Spain
Country of publication:
United States