Stereoselective dienylation of propargylic esters with nucleophiles via transition metal catalysis is a powerful method for accessing conjugated dienes. In particular, divergent synthesis beyond 1,3-dienes can be realized.
A Pd(II)-catalyzed highly regioselective dienylation of sp3 C–H bonds has been accomplished engaging allenes for a variety of aliphatic carboxamides including fatty acids and amino acids.
We have developed a palladium-catalyzed propargylic substitution with alcohols as nucleophiles, wherein monohydric alcohols allow the synthesis of 2-alkoxy-1,3-dienes, while the use of diols allows the formation of 1,4-dioxane derivatives.
Ru(II)-catalyzed highly regioselective annulation of N-pyridyl anilines with allenyl carbinol acetates was demonstrated at room temperature for the facile access to biologically relevant 2-vinylindole derivatives.
This review analyses recent advances and strategies employed in the Pd-AAA of nucleophilic prochiral heterocycles. Each section is focused on a specific heterocycle, where optimisation data and reaction scope have been carefully analysed.