Organic Letters
Letter
(3) Selected examples of nonracemic cyclohexa-2,4-dienones:
(a) Uyanik, M.; Yasui, T.; Ishihara, K. Angew. Chem., Int. Ed. 2013, 52,
9215. (b) Dohi, T.; Takenaga, N.; Nakae, T.; Toyoda, Y.; Yamasaki, M.;
Shiro, M.; Fujioka, H.; Maruyama, A.; Kita, Y. J. Am. Chem. Soc. 2013,
increase of the amount of iodane (1.10 equiv), led to some
diastereoselectivity improvement with dr values up to 80:20, but
these conversions required a much longer reaction time (Table 1,
entries 3−5). It is again the use of the CH2Cl2/TFA solvent
system that gave the best results, allowing us to step up close to a
dr of 90:10 (entries 6−8). In this solvent system, the HPD/
[4+2]-cascade reaction of (+)-curcuphenol (S)-1e using the
bis(λ5-iodane) (S,S)-8a was best performed at −45 °C for 2 h to
furnish the natural “allS” (−)-bacchopetiolone 3e in 68% isolated
yield and with an excellent dr of 91:9 (Table 1, entry 7).
In summary, we have accomplished the first total, biomimetic,
and diastereoselective synthesis (in five steps with 23% overall
yield from acetophenone 4) of the bis(sesquiterpene)
(−)-bacchopetiolone, whose structure and biosynthetic filiation
could hence be revised to the “allS” diastereomer 3e derived from
(+)-curcuphenol (S)-1e. This achievement was made possible
thanks to the development of readily accessible chiral Salen-type
bis(λ5-iodanes), among which the cyclohexyl-based reagent
(S,S)-8a was used to promote the focal asymmetric HPD/[4+2]-
cascade step of this synthesis.
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135, 4558. (c) Pouysegu, L.; Chassaing, S.; Dejugnac, D.; Lamidey, A.-
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(4) Recent reports on chiral iodanes: (a) Berthiol, F. Synthesis 2015, 47,
587. (b) Harned, A. M. Tetrahedron Lett. 2014, 55, 4681. (c) Zhdankin,
V. V. Hypervalent Iodine Chemistry − Preparation, Structure, and Synthetic
Applications of Polyvalent Iodine Compounds; Wiley: Chichester, 2013.
(d) Parra, A.; Reboredo, S. Chem. - Eur. J. 2013, 19, 17244. (e) Uyanik,
M.; Ishihara, K. Yuki Gosei Kagaku Kyokaishi 2012, 70, 1116. (f) Liang,
H.; Ciufolini, M. A. Angew. Chem., Int. Ed. 2011, 50, 11849. (g) Farid, U.;
Wirth, T. Stereoselective Synthesis with Hypervalent Iodine Reagents.
In Asymmetry Synthesis II: More Methods and Applications, Christmann,
M., Brase, S., Eds.; Wiley-VCH: Weinheim, 2012; p 197.
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(5) (a) Bergner, M.; Duquette, D. C.; Chio, L.; Stoltz, B. M. Org. Lett.
2015, 17, 3008. (b) Ren, X.-D.; Zhao, N.; Xu, S.; Lu, H.-N.; Ma, S.-G.;
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Liu, Y.-B.; Li, Y.; Qu, J.; Yu, S.-S. Tetrahedron 2015, 71, 4821.
(c) Pouyseg
A. J.; Quideau, S. Org. Lett. 2008, 10, 5211. (d) Gagnepain, J.; Mer
R.; Dejugnac, D.; Leger, J.-M.; Castet, F.; Deffieux, D.; Pouysegu, L.;
Quideau, S. Tetrahedron 2007, 63, 6493. (e) Lebrasseur, N.; Gagnepain,
J.; Ozanne-Beaudenon, A.; Leger, J.-M.; Quideau, S. J. Org. Chem. 2007,
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u, L.; Marguerit, M.; Gagnepain, J.; Lyvinec, G.; Eatherton,
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eau,
ASSOCIATED CONTENT
* Supporting Information
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The Supporting Information is available free of charge on the
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72, 6280. (f) Gagnepain, J.; Castet, F.; Quideau, S. Angew. Chem., Int. Ed.
2007, 46, 1533. (g) Gagnepain, J.; Castet, F.; Quideau, S. Angew. Chem.,
Experimental procedures and full compound character-
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Int. Ed. 2008, 47, 628. (h) Quideau, S.; Pouysegu, L.; Deffieux, D.;
1
ization, including H and 13C NMR spectra for all new
Ozanne, A.; Gagnepain, J.; Fabre, I.; Oxoby, M. Arkivoc 2003, 6, 106.
(i) Magdziak, D.; Rodriguez, A. A.; Van De Water, R. W.; Pettus, T. R. R.
Org. Lett. 2002, 4, 285.
compounds; HPLC traces; computational results (PDF)
Crystallographic data of 3e′ (CIF)
(6) (a) Bosset, C.; Coffinier, R.; Peixoto, P. A.; El Assal, M.; Miqueu,
K.; Sotiropoulos, J.-M.; Pouyseg
2014, 53, 9860. (b) Quideau, S.; Lyvinec, G.; Marguerit, M.; Bathany,
K.; Ozanne-Beaudenon, A.; Buffeteau, T.; Cavagnat, D.; Chenede, A.
Angew. Chem., Int. Ed. 2009, 48, 4605. (c) Boppisetti, J. K.; Birman, V. B.
Org. Lett. 2009, 11, 1221. (d) Dong, S.; Zhu, J.; Porco, J. A., Jr. J. Am.
Chem. Soc. 2008, 130, 2738.
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u, L.; Quideau, S. Angew. Chem., Int. Ed.
AUTHOR INFORMATION
Corresponding Authors
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Author Contributions
§R.C. and M.E.A. contributed equally to this work.
(7) Ozanne, A.; Pouyseg
Org. Lett. 2003, 5, 2903.
(8) (a) Zdero, C.; Bohlmann, F.; Niemeyer, H. M. Phytochemistry
1991, 30, 1597. (b) Berube, A.; Drutu, I.; Wood, J. L. Org. Lett. 2006, 8,
5421.
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u, L.; Depernet, D.; Franco̧ is, B.; Quideau, S.
Notes
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The authors declare no competing financial interest.
(9) (a) Du, Z.; Li, Y.; Wang, Y.; Ding, L.; Gao, J. Synth. Commun. 2010,
40, 1920. (b) Montiel, L. E.; Zepeda, L. G.; Tamariz, J. Helv. Chim. Acta
2010, 93, 1261. (c) Palais, L.; Alexakis, A. Chem. - Eur. J. 2009, 15, 10473.
(10) Crystallographic data CCDC-993815 (3e′) can be obtained free
of charge from the Cambridge Crystallographic Data Centre.
(11) Trost, B. M.; Crawley, M. L. Chem. Rev. 2003, 103, 2921.
(12) (a) Zhdankin, V. V.; Protasiewicz, J. D. Coord. Chem. Rev. 2014,
275, 54. (b) Zhdankin, V. V.; Koposov, A. Y.; Netzel, B. C.; Yashin, N.
V.; Rempel, B. P.; Ferguson, M. J.; Tykwinski, R. R. Angew. Chem., Int.
Ed. 2003, 42, 2194.
(13) Katritzky, A. R.; Gallos, J. K.; Dupont Durst, H. Magn. Reson.
Chem. 1989, 27, 815.
(14) In situ generation of these iodanes could bypass their lack of
stability in solution, but terminal oxidants (e.g., m-CPBA, DMDO)
commonly used in catalytic processes are not compatible with
oxygenation-sensitive 2-alkylphenols; see ref 6a.
ACKNOWLEDGMENTS
Financial support from the Agence Nationale de la Recherche
(ANR-10-BLAN-0721), the Minister
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e de la Recherche, the
CNRS, and the Conseil Reg
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ional d’Aquitaine, including doctoral
scholarships for R.C., M.E.A., and C.B., is gratefully acknowl-
edged. We thank Simafex (France) for providing us with SIBX,
Dr. J. Brioche (Univ. Rouen, COBRA, CNRS-UMR 6014) for
fruitful discussions on the Salen-type bis(iodoarenes), and P.-H.
Brochard (Univ. Bordeaux, Master student) for his contribution
to the synthesis of curcuphenol.
REFERENCES
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