Facile Synthesis of Z-Alkenes via Uphill Catalysis
摘要:
Catalytic access to thermodynamically less stable Z-alkenes has recently received considerable attention. These approaches have relied upon kinetic control of the reaction to arrive at the thermodynamically less stable geometrical isomer. Herein, we present an orthogonal approach which proceeds via photochemically catalyzed isomerization of the thermodynamic E-alkene to the less stable Z-isomer which occurs via a photochemical pumping mechanism. We consider two potential mechanisms. Importantly, the reaction conditions are mild, tolerant, and operationally simple and will be easily implemented.
Allylic C–H amination is currently accomplished with (sulfon)amides or carbamates. Here we show the first allylicamination that can directly afford alkyl allylamines, enabled by the reactivity of thianthrene-based nitrogen sources that can be prepared from primary amines in a single step.