An unprecedented Sc­(OTf)3-catalyzed C2-selective cyanation/defluorination cascade of perfluoroalkylated 3-indolylmethanols with TMSCN is described, which provides a novel and practical strategy for the synthesis of structurally diverse 3-(2-cyano)-indolyl substituted gem-difluoroalkenes and β-fluoro-β-perfluoroalkylalkenes. The reaction features excellent regio- and stereoselectivity and broad substrate scope. Notably, the obtained gem-difluoroalkenes and β-fluoro-β-perfluoroalkylalkenes could be easily transformed into 3-fluoro­(perfluoroalkyl)-β-carbolines with excellent efficiency simply by treating them with Grignard reagents or DIBAL-H under mild reaction conditions.

A method to chemo- and stereoselectively assemble polycyclic bridged-pyrrolidines and -azepines that relies on the gold(I)-catalyzed cascade annulation of skipped 1,4-diene-tethered 2-alkynylbenzaldehydes is described. The divergence in product selectivity was...

A synthetic method for the chemodivergent assembly of a diverse range of highly functionalized and architecturally challenging cyclohepta[b]indolines that relies on the PtI4-catalyzed oxidative and hydrogenative dearomative [3 + 2]...

An efficient method for the expeditious synthesis of the architecturally challenging biaryl-bridged 8–11 membered N-heterocycles that relies on gold(I)-catalyzed intramolecular [4 + 2] benzannulation of N-tethered diynyl benzaldehydes is described....