New heteroannulation reactions of N-alkoxybenzamides by Pd(II) catalyzed C-H activation.

A new palladium(II) catalyzed methodology for the direct synthesis of alkylidene isoindolinones from N-alkoxybenzamides is presented. Isoindolinone formation proceeds through a highly efficient and E-selective C-H activation/Heck/Aza-Wacker sequence. Substoichiometric amounts of benzoquinone can be employed in a cooperative oxidation system with O(2), leading to facile purification of products.

2,2-Difunctionalization of alkenes via Pd(II)-catalyzed aza-Wacker reactions.

N-Ts and N-Boc derivatives of 1,2-diamines and 1,2-amino alcohols are shown to undergo efficient Pd(II)-catalyzed aza-Wacker reactions with a large range of electron-deficient alkenes. The resulting enamine intermediate generally undergoes cyclization with the second heteroatom to form 1,3-heterocycles. The sequence facilitates the rapid synthesis of saturated oxazolidines, imidazolidines, and their derivatives.