ACS Catalysis
Letter
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Chem. 2010, 12, 1628−1633 See also ref 1b for early studies.
cyclohexenones in good to excellent yield, and its functional
group tolerance has been demonstrated and compares favorably
to that of classical redox isomerizations. Mechanistic studies
have shown that the reaction involves a stereospecific,
intramolecular 1,3-hydride shift and that each diastereomer
can take part in an enantioselective isomerization. These
findings lay the basis for the development of a highly
enantioselective version. Efforts are underway in our laboratory
to discover additional applications of this reaction.
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3118. (b) Mantilli, L.; Mazet, C. Tetrahedron Lett. 2009, 50, 4141−
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C. J. Am. Chem. Soc. 2015, 137, 10720−10727 See also ref 1b for early
studies.
ASSOCIATED CONTENT
■
S
* Supporting Information
Tables S1 and S2, detailed experimental protocols, compound
characterization data and copies of H and 13C NMR spectra.
1
(7) Notable exceptions are the industrial processes for the synthesis
The Supporting Information is available free of charge on the
́
of hydrocodone and hydromorphone: (a) Gomez, A. B.; Holmberg,
P.; Backvall, J.-E.; Martín-Matute, B. RSC Adv. 2014, 4, 39519−39522.
̈
́
(b) Diaz-Alvarez, A. E.; Cadierno, V. Recent Pat. Catal. 2012, 1, 43−50
and references cited therein.
(8) (a) Malanga, C.; Menicagli, R.; Dell’Innocenti, M.; Lardicci, L.
Tetrahedron Lett. 1987, 28, 239−340. (b) Curran, D. P.; Jacobs, P. B.;
Elliott, R. L.; Kim, B. H. J. Am. Chem. Soc. 1987, 109, 5280−5282.
(c) Kitamura, M.; Manabe, K.; Noyori, R.; Takaya, H. Tetrahedron
Lett. 1987, 28, 4719−4720.
AUTHOR INFORMATION
Corresponding Author
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Author Contributions
(9) We are aware of one isolated example of the conversion of a
cyclohexa-2,5-dienol to a cyclohexenone by redox isomerization, in ref
6a.
‡S.K. and T.J. contributed equally.
Notes
(10) An alternate sequence to obtain γ,γ-disubstituted cyclo-
hexenones would involve a selective 1,4-reduction of cyclohexadie-
nones. We obtained at best moderate selectivity in that process. See
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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This work was supported financially by the Natural Sciences
and Engineering Research Council of Canada (NSERC), the
University of Toronto and Alphora Research Inc. S.K.
acknowledges generous financial support from the Deutsche
Forschungsgemeinschaft (DFG) for a postdoctoral research
fellowship. T.J. thanks NSERC and the Fonds de recherche du
(12) Selected examples of their use in total synthesis: (a) Nicolaou,
K. C.; Li, A.; Edmonds, D. J.; Tria, G. S.; Ellery, S. P. J. Am. Chem. Soc.
2009, 131, 16905−16918. (b) Petrova, K. V.; Mohr, J. T.; Stoltz, B. M.
Org. Lett. 2009, 11, 293−295. (c) Liu, G.; Mei, G.; Chen, R.; Yuan, H.;
Yang, Z.; Li, C. Org. Lett. 2014, 16, 4380−4383.
(13) For a relevant discussion of redox isomerization mechanisms,
see ref 4a.
Queb
thank Dr. Ced
discussions and experimental assistance.
́
ec (FRQNT) for graduate scholarships. The authors
ric Burki (University of Toronto) for helpful
́
̈
(14) Clark, H. C.; Kurosawa, H. Inorg. Chem. 1973, 12, 1566−1570.
(15) Batuecas, M.; Esteruelas, M. A.; García-Yerba, C.; Onate, E.
̃
Organometallics 2010, 29, 2166−2175.
(16) Trost, B. M.; Kulawiec, R. J. J. Am. Chem. Soc. 1993, 115, 2027−
2036.
REFERENCES
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ACS Catal. 2016, 6, 747−750