Pd catalysis provides a convenient method for the generation of zwitterionic intermediates that offer significant opportunities for the synthesis of functionalized heterocycles. The combination of electrophilic π-allyl Pd fragments and C-, N- and O-centered nucleophiles allows these intermediates to react with readily available substrates to furnish a range of high value products with control of chemo-, regio- and stereo-selectivity.

3-Fluoro- and trifluoromethylthio-piperidines represent important building blocks for discovery chemistry. We report a simple and efficient method to access analogs of these compounds that are armed with rich functionality allowing them to be chemoselectively derivatized with high diastereocontrol.

Sydnone‐based cycloaddition reactions are a versatile platform for pyrazole synthesis, however they operate under harsh conditions (high temperature and long reaction times). Herein we report a strategy that addresses this limitation utilizing the synergistic combination of organocatalysis and visible‐light photocatalysis. This new approach proceeds under ambient conditions and with excellent levels of regiocontrol. Mechanistic studies suggest that photoactivation of sydnones, rather than enamines, is key to the successful implementation of this process.

Pd catalysis provides a convenient method for the generation of zwitterionic intermediates that offer significant opportunities for the synthesis of functionalized heterocycles. The combination of electrophilic π‐allyl Pd fragments and C‐, N‐ and O‐centered nucleophiles allows these intermediates to react with readily available substrates to furnish a range of high value products with control of chemo‐, regio‐ and stereo‐selectivity. For more details see the Review article by J. P. A. Harrity et al. on page 13830 ff.