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Oxidative 1,2- and 1,3-Alkyl Shift Processes: Developments and Applications in Synthesis

2012; American Chemical Society; Volume: 77; Issue: 5 Linguagem: Inglês

10.1021/jo300169k

1520-6904

Kimiaka C. Guérard, Amandine Guérinot, Cloé Bouchard‐Aubin, Marc-André Ménard, Mathieu L. Lepage, Marc André Beaulieu, Sylvain Canesi,

Chemical synthesis and alkaloids

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 sp2 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. The products represent the central cores of several natural products having important bioactivities. As an illustration of the potential of this method, we describe the rapid synthesis of several functionalized polycyclic systems as well as a formal synthesis of acetylaspidoalbidine, a hexacyclic alkaloid belonging to the Aspidosperma family.