Organometallics
Communication
(22) Fujita, K.-i.; Tanaka, Y.; Kobayashi, M.; Yamaguchi, R. J. Am.
Chem. Soc. 2014, 136, 4829.
(23) Kawahara, R.; Fujita, K.-i.; Yamaguchi, R. J. Am. Chem. Soc.
intermediate during catalysis, and detection of H2 as a reaction
byproduct supports an acceptorless alcohol dehydrogenation
mechanism. This chemistry allows easy access to several
glucocorticoid derivatives, which may be useful in studies of
steroid metabolism29,41 or as possible chemotherapeutics43,44,49
and drug conjugates.50−52 Future investigations will explore the
underlying reasons for chemoselectivity as well as the generality
of this behavior in related catalyst systems.
2012, 134, 3643.
(24) Zeng, G.; Sakaki, S.; Fujita, K.-i.; Sano, H.; Yamaguchi, R. ACS
Catal. 2014, 4, 1010.
(25) Fujita, K.-i.; Ito, W.; Yamaguchi, R. ChemCatChem 2014, 6, 109.
(26) DePasquale, J.; Nieto, I.; Reuther, L. E.; Herbst-Gervasoni, C. J.;
Paul, J. J.; Mochalin, V.; Zeller, M.; Thomas, C. M.; Addison, A. W.;
Papish, E. T. Inorg. Chem. 2013, 52, 9175.
(27) Shen, S.-S.; Kartika, V.; Tan, Y. S.; Webster, R. D.; Narasaka, K.
Tetrahedron Lett. 2012, 53, 986.
ASSOCIATED CONTENT
* Supporting Information
Text and figures giving experimental procedures and physical
methods, GC plots, schemes, and NMR data. This material is
■
S
(28) Cosner, C. C.; Cabrera, P. J.; Byrd, K. M.; Thomas, A. M. A.;
Helquist, P. Org. Lett. 2011, 13, 2071.
(29) Okihara, R.; Mitamura, K.; Hasegawa, M.; Mori, M.; Muto, A.;
Kakiyama, G.; Ogawa, S.; Iida, T.; Shimada, M.; Mano, N.; Ikegawa, S.
Chem. Pharm. Bull. 2010, 58, 344.
(30) Mantilli, L.; Mazet, C. Tetrahedron Lett. 2009, 50, 4141.
(31) Bouziane, A.; Carboni, B.; Bruneau, C.; Carreaux, F.; Renaud, J.-
L. Tetrahedron 2008, 64, 11745.
AUTHOR INFORMATION
Corresponding Author
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́
(32) Cadierno, V.; García-Garrido, S. E.; Gimeno, J.; Varela-Alvarez,
Notes
A.; Sordo, J. A. J. Am. Chem. Soc. 2006, 128, 1360.
(33) Kanaya, S.; Imai, Y.; Komine, N.; Hirano, M.; Komiya, S.
Organometallics 2005, 24, 1059.
The authors declare no competing financial interest.
(34) Daugulis, O.; Brookhart, M. Organometallics 2004, 23, 527.
(35) DePasquale, J.; Kumar, M.; Zeller, M.; Papish, E. T.
Organometallics 2013, 32, 966.
(36) Yamakawa, M.; Ito, H.; Noyori, R. J. Am. Chem. Soc. 2000, 122,
1466.
(37) Wang, W.-H.; Hull, J. F.; Muckerman, J. T.; Fujita, E.; Himeda,
Y. Energy Environ. Sci. 2012, 5, 7923.
(38) Fujita, K.-i.; Yoshida, T.; Imori, Y.; Yamaguchi, R. Org. Lett.
2011, 13, 2278.
ACKNOWLEDGMENTS
■
We thank Dr. Lianpeng Tong and Prof. Randy Thummel (UH)
for help with H2 gas analysis and the University of Houston
new faculty startup grant for funding this work.
REFERENCES
■
(1) Dobereiner, G. E.; Crabtree, R. H. Chem. Rev. 2010, 110, 681.
(2) Gunanathan, C.; Milstein, D. Science 2013, 341, 1229712.
(3) Haack, K.-J.; Hashiguchi, S.; Fujii, A.; Ikariya, T.; Noyori, R.
Angew. Chem., Int. Ed. 1997, 36, 285.
(4) Dobson, A.; Robinson, S. D. Inorg. Chem. 1977, 16, 137.
(5) Noyori, R.; Ohkuma, T. Angew. Chem., Int. Ed. 2001, 40, 40.
(6) Nielsen, M.; Kammer, A.; Cozzula, D.; Junge, H.; Gladiali, S.;
Beller, M. Angew. Chem., Int. Ed. 2011, 50, 9593.
(39) Ward, D. E.; Rhee, C. K.; Zoghaib, W. M. Tetrahedron Lett.
1988, 29, 517.
(40) Walker, E. R. H. Chem. Soc. Rev. 1976, 5, 23.
(41) Yazdi, M. T.; Arabi, H.; Faramarzi, M. A.; Ghasemi, Y.; Amini,
M.; Shokravi, S.; Mohseni, F. A. Phytochemistry 2004, 65, 2205.
(42) Gardi, R.; Vitali, R.; Ercoli, A.; Klyne, W. Tetrahedron 1965, 21,
179.
(43) Pokhrel, M.; Ma, E. Molecules 2011, 16, 9868.
(44) Varela, C.; Tavares da Silva, E. J.; Amaral, C.; Correia da Silva,
G.; Baptista, T.; Alcaro, S.; Costa, G.; Carvalho, R. A.; Teixeira, N. A.
A.; Roleira, F. M. F. J. Med. Chem. 2012, 55, 3992.
(45) The 3α-OH epimer has been reported to be the major isomer
obtained from sodium borohydride reduction of enones in cortisol-
type steroidal compounds. The chemical shift of the H3 proton is
more downshifted in 3α-OH in comparison to that in the 3β-OH
epimer.
(46) Kirk, D. N.; Toms, H. C.; Douglas, C.; White, K. A.; Smith, K.
E.; Latif, S.; Hubbard, R. W. P. J. Chem. Soc., Perkin Trans. 2 1990,
1567.
(47) The H3 signals in the proton NMR spectra of the 3α-OH and
3β-OH epimers of compound 4 appear at 4.06 and 4.01 ppm,
respectively.
(7) Brewster, T. P.; Miller, A. J. M.; Heinekey, D. M.; Goldberg, K. I.
J. Am. Chem. Soc. 2013, 135, 16022.
(8) Blacker, A. J.; Clot, E.; Duckett, S. B.; Eisenstein, O.; Grace, J.;
Nova, A.; Perutz, R. N.; Taylor, D. J.; Whitwood, A. C. Chem.
Commun. 2009, 6801.
(9) Tang, W.; Johnston, S.; Iggo, J. A.; Berry, N. G.; Phelan, M.; Lian,
L.; Bacsa, J.; Xiao, J. Angew. Chem., Int. Ed. 2013, 52, 1668.
(10) Royer, A. M.; Rauchfuss, T. B.; Gray, D. L. Organometallics
2010, 29, 6763.
(11) Song, H.; Kang, B.; Hong, S. H. ACS Catal. 2014, 4, 2889.
(12) Bielinski, E. A.; Lagaditis, P. O.; Zhang, Y.; Mercado, B. Q.;
Wurtele, C.; Bernskoetter, W. H.; Hazari, N.; Schneider, S. J. Am.
Chem. Soc. 2014, 136, 10234.
(13) Zell, T.; Ben-David, Y.; Milstein, D. Angew. Chem., Int. Ed. 2014,
53, 4685.
(14) Moyer, S. A.; Funk, T. W. Tetrahedron Lett. 2010, 51, 5430.
(15) Quintard, A.; Rodriguez, J. Angew. Chem., Int. Ed. 2014, 53,
4044.
(16) Chakraborty, S.; Brennessel, W. W.; Jones, W. J. J. Am. Chem.
Soc. 2014, 136, 8564.
(17) Zhang, G.; Vasudevan, K. V.; Scott, B. L.; Hanson, S. K. J. Am.
Chem. Soc. 2013, 135, 8668.
(18) Johnson, T. C.; Morris, D. J.; Wills, M. Chem. Soc. Rev. 2010, 39,
81.
(19) Nielson, M.; Alberico, E.; Baumann, W.; Drexler, H.-J.; Junge,
H.; Gladiali, S.; Beller, M. Nature 2013, 495, 85.
(20) Brewster, T. P.; Ou, W. C.; Tran, J. C.; Goldberg, K. I.; Hanson,
S. K.; Cundari, T. R.; Heinekey, D. M. ACS Catal. 2014, 4, 3034.
(21) Kawahara, R.; Fujita, K.-i.; Yamaguchi, R. Angew. Chem., Int. Ed.
2012, 51, 12790.
̈
́ ̌ ́
(48) Stefanovic, M.; Lajsic, S. Tetrahedron Lett. 1967, 19, 1777.
(49) Bansal, R.; Acharya, P. C. Chem. Rev. 2014, 114, 6986.
(50) Huxley, M.; Sanchez-Cano, C.; Browning, M. J.; Navarro-
Ranninger, C.; Quiroga, A. G.; Rodger, A.; Hannon, M. J. Dalton
Trans. 2010, 39, 11353.
(51) Sanchez-Cano, C.; Huxley, M.; Ducani, C.; Hamad, A. E.;
Browning, M. J.; Navarro-Ranninger, C.; Quiroga, A. G.; Rodger, A.;
Hannon, M. J. Dalton Trans. 2010, 39, 11365.
(52) Levine, P. M.; Garabedian, M. J.; Kirshenbaum, K. J. Med. Chem.
2014, 57, 8224.
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dx.doi.org/10.1021/om5010258 | Organometallics 2014, 33, 6742−6745