Understanding Site Selectivity in the Palladium-Catalyzed Cross-Coupling of Allenylsilanolates
Scott E Denmark1, Andrea Ambrosi1
1University of Illinois at Urbana-Champaign, Department of Chemistry, 600 S Mathews Ave., Urbana, IL 61801, USA.
Abstract:
Allenylsilanolates can undergo cross-coupling at the α- or γ-terminus, and site selectivity appears to be determined by the intrinsic transmetalation mechanism. Fine-tuning of concentration, nucleophilicity, and steric bulk of the silanolate moiety allows for the selective formation of one isomer over the other. Whereas the α-isomer can be obtained in synthetically useful yield, the γ-isomer is favored only when employing reaction conditions that are inevitably associated with diminished reactivity.
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