Base-Mediated Fragmentation of Bicyclic Dihydro-3,6-oxazines: Transformation of Nitroso Diels–Alder Cycloadducts

Nitroso Diels–Alder cycloadditions of benzene oxide with various acyl-nitroso derivatives are described. Treatment of these cycloadducts with methyllithium results in a fast fragmentation reaction, leading to highly functionalized cyclic amino alcohols. The mechanism of the reaction and the role of the epoxide in the fragmentation process are investigated. The reaction proceeds via the formation of an unsaturated imine, which tautomerizes to an enamine if no neighboring epoxide is present

Iron- and Cobalt-Catalyzed Arylation of Azetidines, Pyrrolidines, and Piperidines with Grignard Reagents

Iron- and cobalt-catalyzed cross-couplings between iodo-azetidines, -pyrrolidines, -piperidines, and Grignard reagents are disclosed. The reaction is efficient, cheap, chemoselective and tolerates a large variety of (hetero)­aryl Grignard reagents