A Pd-catalyzed
1,3-difunctionalization of terminal alkenes using
1,1-disubstituted alkenyl nonaflates and arylboronic acid coupling
partners is reported. This transformation affords allylic arene products
that are difficult to selectively access using traditional Heck cross-coupling
methodologies. The evaluation of seldom employed 1,1-disubstituted
alkenyl nonaflate coupling partners led to the elucidation of subtle
mechanistic features of π-allyl stabilized Pd-intermediates.
Good stereo- and regioselectivity for the formation of 1,3-addition
products can be accessed through a minimization of steric interactions
that emanate from alkenyl nonaflate substitution
