Organic Letters
Letter
Scheme 3. Elaboration of the Key Phenol Precursor
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chairlike transition state 16, Figure 2. Phenol 15 (containing a
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the key intermediate enabling the one-step stereoselective
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formation was triggered by PIFA and occurred in 25% yield
over two steps, Scheme 4 and Figure 2.
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Scheme 4. Oxidative Polycyclization−Pinacol Tandem
Process
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In summary, the main tetracyclic core of a large class of
compounds belonging to the kaurane family has been
enantioselectively synthesized in one step from an elaborated
phenol derivative. This key step is based on a previously
unreported oxidative cascade (tandem polycyclization−pinacol
process) mediated by a hypervalent iodine reagent. This first
example demonstrates the utility of the “aromatic ring
umpolung” concept for the rapid elaboration of complex
polycyclic structures.
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ASSOCIATED CONTENT
Supporting Information
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Experimental procedures, NMR spectra, and characterizations.
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AUTHOR INFORMATION
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Canesi, S. Tetrahedron 2010, 66, 5893. (f) Andrez, J. A.; Giroux, M. A.;
Lucien, J.; Canesi, S. Org. Lett. 2010, 12, 4368. (g) Beaulieu, M. A.;
Sabot, C.; Achache, N.; Guer
010, 16, 11224. (h) Beaulieu, M. A.; Guer
Sabot, C.; Canesi, S. J. Org. Chem. 2011, 76, 9460. (i) Guer
Guerinot, A.; Bouchard-Aubin, C.; Menard, M. A.; Lepage, M.;
́
ard, K. C.; Canesi, S. Chem.Eur. J.
ard, K. C.; Maertens, G.;
ard, K. C.;
Notes
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The authors declare no competing financial interest.
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Beaulieu, M. A.; Canesi, S. J. Org. Chem. 2012, 77, 2121. (j) Jacquemot,
ACKNOWLEDGMENTS
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G.; Canesi, S. J. Org. Chem. 2012, 77, 7588.
We are very grateful to the Natural Sciences and Engineering
Research Council of Canada (NSERC), the Canada Founda-
tion for Innovation (CFI), and the provincial government of
Quebec (FQRNT and CCVC) for their precious financial
support in this research.
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(c) Dohi, T.; Maruyama, A.; Takenaga, N.; Senami, K.; Minamitsuji,
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dx.doi.org/10.1021/ol5024486 | Org. Lett. 2014, 16, 4928−4931