January 2022

Capitalizing on the propensity of 1,2-amino group migration in γ-aminocyclopentenone with a suitable promoter, gem-diaryl-equipped systems unfolded an unprecedented avenue for the Lewis acid promoted displacement of γ-aniline group with nucleophiles such as indole. Such transformation, besides providing a means for direct γ-functionalization of cyclopentenones, presented innumerable scope for β,γ-annulation. Various tailored indolo bisnucleophiles were explored in the current study that rendered an array of indole alkaloid-like compounds in excellent yields and selectivity through one-pot operation. Analysis of collective experimental observation along with designed control experiments strongly suggested the possibility of a retro aza-Piancatelli rearrangement, which is hitherto unknown in the context. Such repertoire could find potential applications in the synthesis of complex assemblies from the Piancatelli rearrangement and related processes.1 Introduction2 Aza-Piancatelli Rearrangement and Related Domino Processes3 An Unprecedented Aza-Piancatelli-Templated Strategy for Polycyclic Assemblies4 Summary and Outlook

We explored the reactivity and substrate scope of the reactions among an alkyl isocyanide, an sp-hybridized reactant (i.e. alkyne or allene), and a carbon cage, as a new approach to functionalize fullerenes and metallofullerenes. This account summarizes the key findings in our recent published work, and some original data for the reaction involving an isocyanide, allenes, and metallofullerene Lu3N@C80.1 Introduction2 Isocyanide-Induced Fullerene/EMF Reactions with Substituted Alkynes3 Isocyanide-Induced Fullerene/EMF Reactions with Substituted Allenes4 Conclusion