Affiliation:
1. Institut de Science et d'Ingénierie Supramoléculaires (ISIS) CNRS UMR 7006 Université de Strasbourg 8 Allée Gaspard Monge 67000 Strasbourg France
2. Department of Chemistry and Biomolecular Sciences University of Ottawa Ottawa Ontario K1N 6N5 Canada
3. Institut Universitaire de France (IUF) 75005 Paris France
Abstract
Abstract1,2‐Diamination of alkenes represents an attractive way to generate differentiated vicinal diamines, which are prevalent motifs in biologically active compounds and catalysts. However, existing methods are usually limited in scope and produce diamines where one or both nitrogens are protected, adding synthetic steps for deprotection and further N‐functionalization to reach a desired target. Furthermore, the range of amino groups that can be introduced at the internal position is fairly limited. Here we describe a 1,2‐diamination of styrenes that directly installs a free amino group at the terminal position and a wide variety of unprotected nitrogen nucleophiles (primary or secondary alkyl or aromatic amines, sulfoximines, N‐heterocycles, and ammonia surrogate) at the internal position. Two complementary sets of conditions encompass electronically activated and deactivated styrenes with diverse substitution patterns and functional groups. Moreover, this strategy can be extended to the 1,2‐aminothiolation of styrenes.