Formation of the Main Cores Present in Natural Products by Tandem Additions.

A rapid route to 5,5- and 5,6- bicyclic systems is provided by an 1,3-alkyl-shift process mediated by a hypervalent iodine reagent on aromatics. The structures obtained contain several unsaturations with different behaviors and reactivities. Such diversity allows further elaborations for the rapid formation of compact systems present in a variety of natural products.

Oxidative 1,2- and 1,3-alkyl shift processes: developments and applications in synthesis.

Oxidative 1,2- and 1,3- alkyl shifts mediated by a hypervalent iodine reagent were performed on simple and inexpensive phenol derivatives. These transpositions enable rapid redesign of the main aromatic skeleton to generate good yields of highly functionalized scaffolds containing a prochiral dienone system, a quaternary carbon center connected to as many as four sp(2) centers, and a carbonyl functionality or precursor. An efficient enantioselective version of this process resulting in the formation of a challenging quaternary carbon center is also described.