ol7b01350_si_001.pdf (2.26 MB)
Diastereoselective Au-Catalyzed Allene Cycloisomerizations to Highly Substituted Cyclopentenes
journal contribution
posted on 2017-06-09, 12:50 authored by Ryan D. Reeves, Alicia M. Phelps, William A. T. Raimbach, Jennifer M. SchomakerSite- and regiocontrolled
Au-catalyzed allene carbocyclizations
furnish highly substituted cyclopentenes in >1:1 dr. Significant substitution on the substrate is tolerated, with potential
to install five contiguous stereocenters after alkene functionalization.
Major challenges include identifying a Au/Cu catalyst that controls
both the relative rates of allene epimerization/cyclization and the
facial selectivity in addition of a metal enolate to the allene. Experiments
to achieve stereodivergent cyclizations and transform key cyclopentenes
into useful synthetic building blocks are described.