- Oxidative 1,2- and 1,3-alkyl shift processes: Developments and applications in synthesis
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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.
- Guerard, Kimiaka C.,Guerinot, Amandine,Bouchard-Aubin, Cloe,Menard, Marc-Andre,Lepage, Mathieu,Beaulieu, Marc Andre,Canesi, Sylvain
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experimental part
p. 2121 - 2133
(2012/05/20)
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- 'Aromatic ring umpolung', a rapid access to the main core of several natural products
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Treatment of various substituted phenols in the presence of (diacetoxyiodo)benzene promotes the formation of a phenoxenium ion, a very electrophilic species able to react with various nucleophiles leading rapidly to a plethora of different cores present i
- Guérard, Kimiaka C.,Sabot, Cyrille,Beaulieu, Marc-André,Giroux, Marc-André,Canesi, Sylvain
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scheme or table
p. 5893 - 5901
(2010/09/09)
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- An unprecedented oxidative wagner - Meerwein transposition
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An oxidative Wagner - Meerwein transposition Involving different functionalities mediated by a hypervalent Iodine reagent has been accomplished. The strategy fits within the concept of "aromatic ring umpolung" and allows rapid access to highly functionali
- Guerard, Kimiaka C.,Chapelle, Clement,Giroux, Marc-Andre,Sabot, Cyrille,Beaulieu, Marc-Andre,Achache, Nabil,Canesi, Sylvain
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supporting information; experimental part
p. 4756 - 4759
(2009/12/27)
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