Agradecimentos: We thank the financial support from the São Paulo Research Foundation (FAPESP, grants 2014/25770-6 and 2013/07600-3), and the Brazilian National Research Council (CNPq, grants 457027/2014-2 and 305387/2013-8). This study was also financed in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior – Brasil (CAPES) – Finance Code 001. R.A.A. would like to thank São Paulo Research Foundation for a postdoctoral fellowship (grant 2019/02052-4). AACB would like to thank FAPESP (grant 2015/01491-3) and CNPq (grant 312550/2020-0) for the financial support Ver menos

Abstract: The chiral aryl lactam nucleus is a common motif present in many bioactive natural products and the development of effective enantioselective methodologies for its preparation is of great interest. In this work, we report the synthesis of several enantioenriched aryl lactams in good yields and enantiomeric ratios using a combined strategy employing arenediazonium salts bearing electron-withdrawing substituents, aryl iodides with electron-donating substituents, and chiral N , N -ligands. The chiral a,ß-unsaturated aryl lactams were obtained in yields of up to 78 % and enantiomeric ratios up to 95 : 5. Furthermore, this work demonstrates the use of chiral N , N -ligands as a viable alternative to the phosphine-based ligands in the enantioselective Heck-Mizoroki reactions using aryl iodides. The origins of the enantioselectivity and the full catalytic cycle for the Heck-Matsuda arylation of the enelactams were investigated through DFT calculations Ver menos