A Key Intermediate in Copper‐Mediated Arene Trifluoromethylation, [nBu4N][Cu(Ar)(CF3)3]: Synthesis,Characterization, and C(sp2)−CF3 Reductive Elimination

The synthesis, characterization, and C(sp²)?CF₃ reductive elimination of stable aryl[tris(trifluoromethyl)]cuprate(III) complexes [nBu₄N][Cu(Ar)(CF₃)₃] are described. Mechanistic investigations, including kinetic studies, studies of the effect of temperature, solvent, and the para substituent of the aryl group, as well as DFT calculations, suggest that the C(sp²)?CF₃ reductive elimination proceeds through a concerted carbon–carbon bond‐forming pathway.     

Asymmetric Total Syntheses of the Akuammiline Alkaloids (−)‐Strictamine and (−)‐Rhazinoline

Strictamine and rhazinoline are representative methanoquinolizidine‐containing akuammiline alkaloids that possess different stereochemistry at the C16 position. A unified approach to the enantioselective total syntheses of these two molecules is described. The key steps in this synthesis include a photocatalytic intra/intermolecular type II radical cascade reaction, a Tsuji–Trost allylation, a palladium‐ or nickel‐mediated cyclization, and a late‐stage intramolecular N‐alkylation reaction.