ACS Catalysis
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T.; Colyer, J. T.; Thiel, O. R.; Seran, M. D.; Larsen, R. D.; Murry, J. A.
robust Mn pincer complex, involves acceptorless dehydro-
genative coupling of an alcohol with hydrazine, followed by
base-mediated Wolff-Kishner reduction of the intermediate
hydrazone. This Mn-catalyzed protocol is functional group
tolerant and selective for different kinds of primary benzylic
and aliphatic alcohols leading to moderate to excellent
yields, even in the presence of electron-withdrawing func-
tionalities and the NH2 group. Moreover, the reaction is
selective to primary alcohols. Further developments aimed at
base-free direct deoxygenation methods using non-noble
metal catalysts are in progress.
J. Org. Chem. 2011, 76, 9519. (e) Dobmeier, M.; Herrmann, J. M.;
Lenoir, D.; König, B. Beilstein J. Org. Chem. 2012, 8, 330. (f) Sawad-
joon, S.; Lundstedt, A.; Samec, J. S. M. ACS Catal. 2013, 3, 635. (g)
Yang, Z.; Kumar, R. K.; Liao, P.; Liu, Z.; Li, X.; Bi, X. Chem. Commun.
2016, 52, 5936.
(9) Selected examples of direct deoxygenation of alcohols using
silanes as hydride sources: (a) Gevorgyan, V.; Liu, J.-X.; Rubin, M.;
Benson, S.; Yamamoto, Y. Tetrahedron Lett. 1999, 40, 8919. (b) Ge-
vorgyan, V.; Rubin, M.; Benson, S.; Liu, J.-X.; Yamamoto, Y. J. Org.
Chem. 2000, 65, 6179. (c) Yasuda, M.; Onishi, Y.; Ueba, M.; Miyai, T.;
Baba, A. J. Org. Chem. 2001, 66, 7741. (d) Nishibayashi, Y.; Shinoda,
A.; Miyake, Y.; Matsuzawa, H.; Sato, M. Angew. Chem., Int. Ed. 2006,
45, 4835. (e) Meyer, V. J.; Niggemann, M. Chem.—Eur. J. 2012, 18,
4687. (f) Egi, M.; Kawai, T.; Umemura, M.; Akai, S. J. Org. Chem.
2012, 77, 7092. (g) Drosos, N.; Morandi, B. Angew. Chem., Int. Ed.
2015, 54, 8814.
(10) (a) Huang, J.-L.; Dai, X.-J.; Li, C.-J. Eur. J. Org. Chem. 2013,
6496. (b) Dai, X.-J.; Li, C.-J. J. Am. Chem. Soc. 2016, 138, 5433.
(11) (a) Catalysis Without Precious Metals, Bullock, R. M., Ed.;
Wiley-VCH: Weinheim, Germany, 2010. (b) Bauer, I.; Knölker, H.-J.
Chem. Rev. 2015, 115, 3170. (c) Su, B.; Cao, Z.-C.; Shi, Z.-J. Acc. Chem.
Res. 2015, 48, 886. (d) Zell, T.; Milstein, D. Acc. Chem. Res. 2015, 48,
1979. (e) Liu, W.; Ackermann, L. ACS Catal. 2016, 6, 3743. (f) Connel-
ly Robinson, S. J.; Heinekey, D. M. Chem. Commun. 2017, 53, 669.
(12) Reviews on MLC: (a) Zhao, B.; Han, Z.; Ding, K. Angew.
Chem., Int. Ed. 2013, 52, 4744. (b) Khusnutdinova, J. R.; Milstein, D.
Angew. Chem., Int. Ed. 2015, 54, 12236.
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ASSOCIATED CONTENT
Supporting Information
Spectroscopic and mechanistic details. This material is avail-
AUTHOR INFORMATION
Corresponding Author
Notes
The authors declare no competing financial interests.
(13) Reviews: (a) Gunanathan, C.; Milstein, D. Acc. Chem. Res.
2011, 44, 588. (b) Gunanathan, C.; Milstein, D. Top. Organomet.
Chem. 2011, 37, 55. (c) Gunanathan, C.; Milstein, D. Chem. Rev. 2014,
114, 12024.
(14) (a) Gunanathan, C.; Milstein, D. Science 2013, 341, 1229712. (b)
Pandey, P.; Dutta, I.; Bera, J. K. Proc. Natl. Acad. Sci., India, Sect. A
Phys. Sci. 2016, 86, 561. (c) Crabtree, R. H. Chem. Rev. 2017, DOI:
10.1021/acs.chemrev.6b00556.
ACKNOWLEDGMENT
This research was supported by the European Research
Council (ERC AdG 692775). J.O.B. thanks the Alexander von
Humboldt Foundation for the awards of a Feodor Lynen
Research and a Return Fellowship. S.C. thanks the Swiss
Society of Friends of the Weizmann Institute of Science for a
generous Postdoctoral Fellowship.
(15) Mukherjee, A.; Nerush, A.; Leitus, G.; Shimon, L. J. W.; Ben-
David, Y.; Espinosa-Jalapa, N. A.; Milstein, D. J. Am. Chem. Soc. 2016,
138, 4298.
REFERENCES
(16) Mn-catalyzed dehydrogenation of alcohols: (a) Mastalir, M.;
Glatz, M.; Gorgas, N.; Stöger, B.; Pittenauer, E.; Allmaier, G.; Veiros,
L. F.; Kirchner, K. Chem.—Eur. J. 2016, 22, 12316. (b) Mastalir, M.;
Glatz, M.; Pittenauer, E.; Allmaier, G.; Kirchner, K. J. Am. Chem. Soc.
2016, 138, 15543. (c) Andérez-Fernández, M.; Vogt, L. K.; Fischer, S.;
Zhou, W.; Jiao, H.; Garbe, M.; Elangovan, S.; Junge, K.; Junge, H.;
Ludwig, R.; Beller, M. Angew. Chem., Int. Ed. 2017, 56, 559; d) Deibl,
N.; Kempe, R. Angew. Chem., Int. Ed. 2017, 56, 1663. (e) Nguyen, D.
H.; Trivelli, X.; Capet, F.; Paul, J.-F.; Dumeignil, F.; Gauvin, R. M. ACS
Catal. 2017, 7, 2022.
(17) Mn-catalyzed hydrogenation reactions: (a) Elangovan, S.;
Topf, C.; Fischer, S.; Jiao, H.; Spannenberg, A.; Baumann, W.; Lud-
wig, R.; Junge, K.; Beller, M. J. Am. Chem. Soc. 2016, 138, 8809. (b)
Kallmeier, F.; Irrgang, T.; Dietel, T.; Kempe, R. Angew. Chem., Int. Ed.
2016, 55, 11806. (c) Elangovan, S.; Garbe, M.; Jiao, H.; Spannenberg,
A.; Junge, K.; Beller, M. Angew. Chem., Int. Ed. 2016, 55, 15364. (d)
Espinosa-Jalapa, N. A.; Nerush, A.; Shimon, L. J. W.; Leitus, G.;
Avram, L.; Ben-David, Y.; Milstein, D. Chem.—Eur. J. 2016, DOI:
10.1002/chem.201604991. (e) Bruneau-Voisine, A.; Wang, D.; Roisnel,
T.; Darcel, C.; Sortais, J.-B. Cat. Commun. 2017, 92, 1.
(18) Mn-catalyzed transfer hydrogenation and hydrogen auto-
transfer reactions: (a) Elangovan, S.; Neumann, J.; Sortais, J.-B.;
Junge, K.; Darcel, C.; Beller, M. Nat. Commun. 2016, 7, 12641. (b)
Pena-López, M.; Piehl, P.; Elangovan, S.; Neumann, H.; Beller, M.
Angew. Chem., Int. Ed. 2016, 55, 14967. (c) Perez, M.; Elangovan, S.;
Spannenberg, A.; Junge, K.; Beller, M. ChemSusChem 2017, 10, 83. (d)
Bruneau-Voisine, A.; Wang, D.; Dorcet, V.; Roisnel, T.; Darcel, C.;
Sortais, J.-B. J. Catal. 2017, 347, 57. (e) Neumann, J.; Elangovan, S.;
Spannenberg, A.; Junge, K.; Beller, M. Chem.—Eur. J. 2017, DOI:
10.1002/chem.201605218.
(1) Reviews: (a) Vennestrøm, P. N. R.; Osmundsen, C. M.; Chris-
tensen, C. H.; Taarning, E. Angew. Chem., Int. Ed. 2011, 50, 10502. (b)
He, M.; Sun, Y.; Han, B. Angew. Chem., Int. Ed. 2013, 52, 9620. (c) Li,
C.-J. Chem. 2016, 1, 423.
(2) Reviews: (a) Furimsky, E. Appl. Catal. A 2000, 199, 147. (b)
Corma, A.; Iborra, S.; Velty, A. Chem. Rev. 2007, 107, 2411. (c) Bozell,
J. J.; Petersen, G. R. Green Chem. 2010, 12, 539. (d) Dam, J. t.; Hane-
feld, U. ChemSusChem 2011, 4, 1017. (e) Ruppert, A. M.; Weinberg, K.;
Palkovits, R. Angew. Chem., Int. Ed. 2012, 51, 2564.
(3) Trost, B. M. Science 1983, 219, 245.
(4) Wender, P. A.; Verma, V. A.; Paxton, T. J.; Pillow, T. H. Acc.
Chem. Res. 2008, 41, 40.
(5) Review on deoxygenation of alcohols: Herrmann, J. M.; König,
B. Eur. J. Org. Chem. 2013, 7017.
(6) Selected examples of two-step deoxygenation of alcohols: (a)
Lopez, R. M.; Hays, D. S.; Fu, G. C. J. Am. Chem. Soc. 1997, 119, 6949.
(b) Zhang, L.; Koreeda, M. J. Am. Chem. Soc. 2004, 126, 13190. (c)
Spiegel, D. A.; Wiberg, K. B.; Schacherer, L. N.; Medeiros, M. R.;
Wood, J. L. J. Am. Chem. Soc. 2005, 127, 12513. (d) Jordan, P. A.; Mil-
ler, S. J. Angew. Chem., Int. Ed. 2012, 51, 2907. (e) Dang, H.; Cox, N.;
Lalic, G. Angew. Chem., Int. Ed. 2014, 53, 752.
(7) (a) Barton, D. H. R.; McCombie, S. W. J. Chem. Soc., Perkin
Trans. 1 1975, 1574. (b) McCombie, S. W.; Motherwell, W. B.; Tozer,
M. J. in Organic Reactions, Vol. 77, Denmark, S. E., Ed.; Wiley: Ho-
boken, New Jersey, 2012, pp. 161-432.
(8) Selected examples of direct deoxygenation of alcohols: (a) Fu-
nabiki, T.; Yamazaki, Y.; Tarama, K. J. Chem. Soc., Chem. Commun.
1978, 63. (b) Myers, A. G.; Movassaghi, M.; Zheng, B. J. Am. Chem.
Soc. 1997, 119, 8572. (c) Diéguez, H. R.; López, A.; Domingo, V.;
Arteaga, J. F.; Dobado, J. A.; Herrador, M. M.; Quílez del Moral, J. F.;
Barrero, A. F. J. Am. Chem. Soc. 2010, 132, 254. (d) Milne, J. E.; Storz,
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