Aziridine- and Azetidine-Pd Catalytic Combinations. Synthesis and Evaluation of the Ligand Ring Size Impact on Suzuki-Miyaura Reaction Issues

Abstract

Abstract:The synthesis of new vicinal diamines based on aziridine and azetidine cores as well as the comparison of their catalytic activities as ligand in the Suzuki-Miyaura coupling reaction are described in this communication. The synthesis of three-and four-membered ring heterocycles substituted by a methylamine pendant arm is detailed from the parent nitrile derivatives. Complexation to palladium under various conditions has been examined affording vicinal diamines or amine-imidate complexes. The efficiency of four new catalytic systems is compared in the preparation of variously substituted biaryls. Aziridine-and azetidine-based catalytic systems allowed Suzuki-Miyaura reactions from aryl halides including chlorides with catalytic loadings until 0.001% at temperatures ranging from 100 • C to r.t. The evolution of the Pd-metallacycle ring strain moving from azetidine to aziridine in combination with a methylamine or an imidate pendant arm impacted the Suzuki-Miyaura reaction issue.

RuO4-Mediated oxidation of N-benzylated tertiary amines. Four- and three-membered azacycloalkanes as substrates

“…2-Cyanoazetidines like 12c are versatile intermediates for a wide variety of catalysts, 21 biological amines, 22 or nitrogen heterocycles. 23 Even if it is out of the scope of this paper, the RuO4-oxidation of 1c under cyanidetrapping conditions (T-7) might be viewed, after further optimization, as a new way to synthesize 2cyanoazetidines and may be added to the already known methods.…”