Agradecimentos: We acknowledge financial support from the São Paulo Research Foundation (FAPESP grants 2014/26378-2, 2014/25770-6, and 2013/07600-3) and the Brazilian National Research Council (CNPq grants 457027/2014-2 and 305387/2013-8). We also thank CNPq for the fellowship to J.V.S (155377/2018-3) and Coordination for the Improvement of Higher Education Person-nel (CAPES) for the fellowship to C.L.H. We also thank Dr. Ricardo. A. Angnes for his help with the crystallographic data and the Ph.D. student Otto D. Koster for the optical rotations analyses of the Heck adducts 5. Ver menos

Abstract: An in tandem enantioselective Heck-Matsuda (HM) reaction of cyclic and acyclic olefins directly from anilines is described. The method relies on a process involving the progressive in situ diazotization of the starting anilines followed by a palladium-catalyzed Heck-Matsuda arylation using chiral N,N-ligands. This intermolecular enantioselective HM arylation strategy was applied to the desymmetrization of three distinct unactivated olefins as proof of concept. The method demonstrates broad substrate scope furnishing the Heck adducts in good to excellent enantiomeric ratios of up to 99:1, high diastereoselectivities (cyclopenten-3-ol with > 20:1 dr), and good overall yields of up to 82% over 2 or 3 steps. Ver menos