Zinc-catalyzed allenylations of aldehydes and ketones.

The general zinc-catalyzed allenylation of aldehydes and ketones with an allenyl boronate is presented. Preliminary mechanistic studies support a kinetically controlled process wherein, after a site-selective B/Zn exchange to generate a propargyl zinc intermediate, the addition to the electrophile effectively competes with propargyl-allenyl zinc equilibration. The utility of the methodology was demonstrated by application to a rhodium-catalyzed [4+2] cycloaddition.
(© 2011 American Chemical Society)