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ACS Catalysis
the Camille and Henry Dreyfus Postdoctoral Program in
Environmental Chemistry, and NIH for a training grant (CBIT
NIGMS T32 GM008505) that supported BLR. NMR
spectroscopy facilities were partially supported by the NSF (CHE-
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208463) and NIH (S10 RR08389).
applying the mixed DBU/NMI catalyst system to the oxidation of
CyCH OH provided higher yields of the corresponding aldehyde
than
2
REFERENCES
1
a
reaction with DBU alone (94% vs. 85%
H NMR
spectroscopy). The initial rates for the two systems were similar
suggesting that employing NMI in addition to DBU helps mitigate
the catalyst deactivation observed when DBU is the only base
present.
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(12) The data cannot exclude equilibrium formation of a L
alkoxide species.
Cu –
n
(
(
1) Tojo, G.; Fernández, M. In Oxidation of Alcohols to Aldehydes
and Ketones; Tojo, G., Ed.; Springer: New York, 2010.
2) (a) Arends, I. W. C. E.; Sheldon, R. A. In Modern Oxidation
Methods; Bäckvall, J.-E., Ed.; Wiley-VCH Verlag Gmb & Co.:
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ten Brink, G.-J.; Dijksman, A. Acc. Chem. Res. 2002, 35, 774-781
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F.; Goblet, D.; Penevaux, A. R.; Luxen, A. J., Angew. Chem. Int.
Ed. 2010, 49, 3161-3164. (b) Kaljurand, I.; Kütt, A.; Sooväli, L.;
Rodima, T.; Mäemets, V.; Leito, I.; Koppel, I. A. J. Org. Chem.
2005, 70, 1019-1028.
(
(
c) Zhan, B. Z.; Thompson, A. Tetrahedron 2004, 60, 2917-2935.
d) Mallat, T.; Baiker, A. Chem. Rev. 2004, 104, 3037-3058 (e)
(
(
(
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Stahl, S. S. Angew. Chem., Int. Ed. 2004, 43, 3400−3420. (f)
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5
258-5261.
16) For additional catalyst systems, see ref. 8 (cf. refs. 9 and 10 in
this publication).
17) See, for example: (a) Sonobe, T.; Oisaki, K.; Kanai, M. Chem.
Sci. 2012, 3, 3249-3255. (b) Han, B.; Yang, X.-L.; Wang, C.; Bai,
Y.-W.; Pan, T.-C.; Chen, X.; Yu, W. J. Org. Chem. 2012, 77,
2
8
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40. (g) Schultz, M. J.; Sigman, M. S. Tetrahedron 2006, 62, 8227-
241. (h) Sigman, M. S.; Jensen, D. R. Acc. Chem. Res. 2006, 39,
21-229. (i) Karimi, B.; Zamani, A. J Iran Chem Soc 2008, 5, S1-
1
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136-1142. (c) Hu, Z.; Kerton, F. M. Org. Biomol. Chem. 2012, 10,
618-1624. (d) Tao, C.; Liu, F.; Zhu, Y.; Liu, W.; Cao, Z. Org.
S20. (j) Matsumoto, T.; Ueno, M.; Wang, N.; Kobayashi, S. Chem-
Asian J 2008, 3, 196-214. (k) Parmeggiani, C.; Cardona, F. Green
Chem. 2012, 14, 547-564.
Biomol. Chem. 2013, 11, 3349-3354. (e) Yin, W.; Wang, C.;
Huang, Y. Org. Lett. 2013, 15, 1850-1853. (f) Dornan, L. M.; Cao,
Q.; Flanagan, J. C. A.; Cook, M. J.; Crawford, M. J.; Muldoon, M.
J. Chem. Commun. 2013, 49, 6030-6032 (g) Kim, J.; Stahl, S. S.
ACS Catal. 2013, 3, 1652-1656.
(
(
3) Semmelhack, M. F.; Schmid, C. R.; Cortés, D. A.; Chou, C. S. J.
Am. Chem. Soc. 1984, 106, 3374-3376.
4) (a) Gamez, P.; Arends, I. W. C. E.; Reedijk, J.; Sheldon, R. A.
Chem. Commun. 2003, 2414-2415. (b) Gamez, P.; Arends, I. W. C.
E.; Sheldon, R. A.; Reedijk, J. Adv. Synth. Catal. 2004, 346, 805-
811.
(
(
5) Kumpulainen, E. T. T.; A. M. P. Koskinen Chem. Eur. J. 2009,
1
5, 10901-10911.
6) Hoover, J. M.; Stahl, S. S. J. Am. Chem. Soc. 2011, 133, 16901-
6910. (b) Hoover, J. M.; Steves, J. E., Stahl, S. S. Nat.
1
Protoc. 2012, 7, 1161-1166 (c) Hoover, J. M.; Stahl, S. S. Org.
Synth. 2013, 90, 2357-2367.
(
7) (a) Ragagnin, G.; Betzemeier, B.; Quici, S. Knochel, P.
Tetrahedron 2002, 58, 3985-3991. (b) Contel, M.; Izuel, C.;
Laguna, M.; Villuendas, P. R.; Alonso, P. J.; Fish, R. H. Chem.
Eur. J. 2003, 9, 4168-4178. (c) Contel, M.; Villuendas, P. R.;
Fernandez-Gallardo, J.; Alonso, P. J.; Vincent, J.-M.; Fish, R. H.
Inorg. Chem. 2005, 44, 9771-9778. (d) Geisslmeir, D.; Jary, W. G.;
Falk, H. Monatsh. Chem. 2005, 136, 1591-1599. (e) Jiang, N.;
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S.; Alamsetti, S. K.; Sekar, G. Adv. Synth. Catal. 2007, 349, 2253-
2
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(
(
8) Hoover, J. M.; Ryland, B. L.; Stahl, S. S. J. Am. Chem. Soc. 2013,
1
35, 2357-2367.
9) For an earlier system that catalyzes oxidation of aliphatic alcohols
see Tretyakov, V. P.; Chudaev, V. V.; Zimtseva, G. P. Ukr. Khim.
Zh. 1985, 51, 942-946
2 2
(10) A crystal structure of [Cu(bpy)(OH)] (OTf) has been previously
reported, although the packing of the dimers within the unit cell is
significantly different. Castro, I.; Faus, J.; Julve, M.; Bois, C.;
Real, J. A.; Lloret, F. J. Chem. Soc. Dalton Trans. 1992, 47-52.
The crystals in the present work consist of dimers of
2+
[
Cu(bpy)(OH)]
2
dimers in which long axial Cu–O bonds (2.4Å)
connect adjacent dimers (Figure S2).
II
(11) With Cu (OTf)
2
, use of both DBU and NMI was shown to afford
higher yields with aliphatic alcohols (see ref. 5). For example,
7
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