Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)We describe herein a highly regio- and enantioselective Pd-catalyzed Heck arylation of unactivated trisubstituted acyclic olefins to provide all-carbon quaternary stereogenic centers. Chiral N,N ligands of the pyrimidine-and pyrazino-oxazoline class were developed for that purpose, providing the desired products in good to high yields with enantiomeric ratios up to > 99:1. Both linear and branched substituents on the olefins were well-tolerated. The potential of this new method is demonstrated by the straightforward synthesis of several O-methyl lactols and lactones containing quaternary stereocenters, together with a concise enantioselective total synthesis of the calcium channel blocker verapamil.5447 1403614039Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Swiss National Science FoundationFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)FAPESP [2013/07600-3, 2014/00588-0]