4
Tetrahedron
undergoes reaction with O
2
and abstract hydrogen from the
CO
Scheme 1b). The reaction of peracetic acid with Cu(I) species
2 2
highly efficiently in acetonitrile/CH Cl at 70˚ C without using
second molecule of acetaldehyde or alkane to produce CH
3
3
H
any expensive ligand as the results of copper based and radical
based reactions. In this system acetonitrile acts not only as a
solvent but also a ligand to generate and stabilize Cu(I) species,
18
(
19
would give copper-oxo speices, which undergoes hydrogen
abstraction from alkane, and oxygen rebound to give the
corresponding alcohol (Scheme 1c). The alcohol is oxidized to
the corresponding ketone under the reaction conditions. The
acyl radical thus formed undergoes hydrogen abstraction from
alkanes to give alkyl radical which undergoes reaction with
molecular oxygen, giving alkylperoxyl radical. Termination
would give ketones and alcohols (Scheme 1d). Leitner et al.
demonstrated that selective oxidation of alkanes with molecular
oxygen and acetaldehyde in compress carbon dioxide proceeds
thus offering
a
new possibility for selective C-H
functionalization of unreactive hydrocarbons.
References and notes
1.
(a) Shilov, A. E.; Shul’pin, G. B. Chem. Rev. 1997, 97, 2879. (b)
Ishii, Y.; Sakaguchi, S.; Iwahama, T. Adv. Synth. Cat. 2001, 343,
3
2
4
93. (c) Sheldon, R. A.; Arends, I. W. C. E. Adv. Synth. Catal.
004, 346, 1051. (d) Hill, C. L. Angew. Chem. Int. Ed., 2004, 43,
02. (e) Punniyamurthy, T.; Velusamy, S.; Iqbal, J. Chem. Rev.,
2005, 105, 2329. (f) Yeung. C. S.; Dong, V. M. Chem. Rev. 2011,
111, 1215. (g) Wendlandt, A. E.; Suess, A. M.; Stahl, S. S.
Angew. Chem. Int. Ed, 2011, 50, 11062. (h) Newhouse, T.;
Baran, P. S. Angew. Chem. Int. Ed. 2011, 50, 3362. (i) Bäckvall,
3a
highly efficiently, where alkylperoxy radical plays a key role.
In the copper-catalyzed aerobic oxidation of benzylic C-H bond
the copper-promoted formation acyl radical and Scheme (d)
would occur.
nd
J.-E., Modern Oxidation methods, 2 ed., Wiley-VCH,
Weinheim, 2011.
2
3
.
.
Austin, R. N. Groves, J. T. Metallomics 2011, 3, 775.
(a) Theyssen, N.; Hou, Z.; Leitner, W. Chem. Eur. J. 2006, 12,
3401. (b) Contel, M.; Izuel, C.; Laguna, M.; Villuendas, P. R.;
Alonso, P. J. ; Fish, R. H. Chem. Eur. J. 2003, 9, 4168. (c) Lee, J.
M.; Park, E. J.; Cho, S. H.; Chang. S. J. Am. Chem. Soc. 2008,
130, 7824. (d) Chan, S. I.; Yu, S. S.-F. Acc. Chem. Res. 2008, 41,
CuII
CuI
Cu0
(
(
a)
CH3CN
CH3CN
b) CH CHO
+
CuII
CH CO
+
CuI
+
H+
3
3
9
69. (e) Mishra, G. S.; Kumar, A.; Tavares, P. B. J. Mol. Cat. A
CH CO
+
O2
CH CHO
CH CO3
3
3
2012, 357, 125. (f) Gephart, R. T., III; McMullin, C. L.;
Sapiezynski, N. G.; Jang, E. S.; Aguila, M. J.; Cundari, T. R.;
Warren, T. H. J. Am. Chem. Soc. 2012, 134, 17350.
CH CO
+
CH CO H + CH CO
3
3
3
3
3
3
c) CuI
II
4.
(a) Murahashi. S. I. Angew. Chem., Int. Ed. Engl. 1995, 34, 2443.
(
+
CH3CO3H
R-H
R-H
Cu -O
Cu -OH + R
CH CHO + R
+ CH3CO2H
(
b) Murahashi, S.-I.; Imada, Y. Transition Metals for Organic
Synthesis; Beller, M.; Bolm, C., Eds.; Wiley-VCH, Weinheim,
004; Vol 2, pp. 497–507. (c) Murahashi, S.-I., Komiya, N.,ref 1i,
II
II
CuI
Cu -O
+
+
R-OH
2
p 241-276. (d) Murahashi, S.-I., Komiya, N., Ruthenium in
Organic Synthesis, Wiley-VCH, Weinheim, Murahashi, S.-I. Ed.,
(
d) CH CO
+
3
3
2
004, pp 53-94. (e) Murahashi, S.-I.; Zhang, D. Chem. Soc. Rev.
R
2
+ O2
ROO
R=O + R-OH
2008, 37, 1490.
5
6
.
.
(a) Murahashi, S.-I.; Komiya, N.; Oda, Y.; Kuwabara, T.; Naota,
T. J. Org. Chem. 2000, 65, 9186. (b) Nakanishi, M.; Bolm, C.
Adv. Synth. Catal. 2007, 349, 861, and references cited therein.
C-H oxidation, (a) Komiya, N.; Noji, S.; Murahashi, S.-I. Chem.
Commun. 2001, 65. (b)Murahashi, S.-I.; Oda, Y.; Komiya, N.;
Naota, T. Tetrahedron Lett. 1994, 35, 7953. Epoxidation, (c)
Murphy, A.; Dubois, G. Stack, T. D. P. J. Am. Chem. Soc. 2003,
ROO
+
O2
Scheme 1. Proposed mechanism for aerobic oxidation of alkanes. (a)
Formation of Cu(I) species in CH CN. (b) Copper-promoted
3
autoxidation of acetaldehyde to give peracetic acid. (c) Formation of
copper-oxo species followed by oxidation of alkanes. (d) Acyl radical-
mediated oxidation.
1
25, 5250. (d) Fujita, M.; Que, L., Jr. Adv. Synth. Catal, 2004,
346, 190. (e) Garcia-Bosch, I.; Company, A.; Fontrodona, X.;
Ribas, X.; Costas, M. Org. Lett. 2008, 10, 2095.
7
.
(a) Murahashi, S.-I.; Saito, I.; Naota, T.; Kumobayashi, H.;
Akutagawa, S. Tetrahedron Lett. 1991, 32, 5991. ( b) Murahashi,
S.-I.; Oda, T.; Naota, T. Tetrahedron Lett. 1992, 33, 7557.
Murahashi, S.-I.; Naota, T.; Komiya, N. Tetrahedron Lett. 1995,
36, 8059.
Combination of the palladium-catalyzed oxidation of
ethylene, which is obtained readily from shale gas, with
molecular oxygen (Wacker reaction) and the present copper-
catalyzed oxidation of alkanes with molecular oxygen in the
presence of acetaldehyde would provide a powerful and atom-
economical strategy for the oxidative functionalization of
8
9
.
.
(a) Komiya, N.; Naota, T.; Oda, Y.; Murahashi, S.-I. J. Mol.
Catal. A. 1997, 117, 21. (b) Rudler, H.; Denise, B. J. Mol. Cat. A.
2
000, 154, 277.
1
0. (a) Kaim, W.; Rall, J. Angew. Chem. Int. Ed. Engl. 1996, 35, 43,
and references cited therein. (b) Itoh, S.; Fukuzumi, S. Acc.
Chem. Res. 2007, 40, 592. (c) Cramer, C. J.; Tolman, W. B. Acc.
Chem. Res. 2007, 40, 601. (d) Copper-Oxygen Chemistry,
Karlin, K. D.; Itoh, S., Eds. John Wiley & Sons: Hoboken, New
Jersey, 2011. (e) Liu, Z.-Q.; Zhao, L.; Shang, X.; Cui, Z. Org.
Lett. 2012, 14, 3218. (f) Mirica, L. M.; Ottenwaelder, X.: Stack, T.
D. P. Chem. Rev. 2004, 104, 1013.
hydrocarbons R
products (Scheme 2).
2
CH
2
with molecular oxygen to give oxidation
Pd cat.
H2C CH2
+
1/2 O2
CH CHO
3
1
1. Murahashi, S.-I.; Oda, Y.; Naota, T. J. Am. Chem. Soc. 1992, 114,
7
913.
Cu cat.
3/2 O2
R2CH2
+
CH3CHO
H2C CH2
+
+
R2CO
R2CO
+
+
CH3CO2H
CH3CO2H
+
+
H2O
H2O
12. Murahashi, S.-I.; Zhou, X.-G.; Komiya, N. Synlett 2003, 321. (a)
3. Murahashi, S.-I.; Oda, Y.; Naota, T.; Komiya, N. J. Chem. Soc.,
Chem. Commun. 1993, 139.
4. Yanagihara, N.; Ogura, T. Trans. Metal Chem. 1987, 12, 9.
5. High-pressure oxidation reactions were performed in a high
1
1
1
R2CH2
+
2 O2
Scheme 2.
2
pressure system with a constant stream of 1 atm of O . A glass
autoclave (96 mL) with hastelloy attachment (Hyper-glass
cylinder HPG96-3, Taiatsu Techno Corporation, Japan) with a
glass inner reaction vessel was charged with reaction solutions.
In conclusion, the aerobic copper-catalyzed oxidation of
alkanes with an equivalent of acetaldehyde can be performed
2
The autoclave was pressurized to 1 atm of O diluted with 8 atm
of N , and the mixture was stirred at 70 ˚C.
2