Total synthesis of (+/-)-cytisine via the intramolecular heck cyclization of activated N-alkyl glutarimides

[reaction:see text] A synthesis of racemic cytisine 1 has been developed utilizing an intramolecular Heck cyclization to prepare the bridged tricyclic intermediate 2. The cyclization employs activated glutarimide-derived ketene aminals 3 (X = P(O)OEt(2) or SO(2)CF(3)) and represents the first use of such intermediates in metal-catalyzed processes.     

Recent Advances in Visible Light-Mediated Radical Fluoro-alkylation, -alkoxylation, -alkylthiolation, -alkylselenolation,and -alkylamination

In the last few years, many reagents and protocols have been developed to allow for the efficient fluorofunctionalization of a diverse set of scaffolds ranging from alkanes, alkenes, alkynes, and (hetero)arenes. The concomitant rise of organofluorine chemistry and visible light-mediated synthesis have synergistically expanded the fields and have mutually benefitted from developments in both fields. In this context, visible light driven formations of radicals containing fluorine have been a major focus for the discovery of new bioactive compounds. This review details the recent advances and progress made in visible light-mediated fluoroalkylation and heteroatom centered radical generation.