J . Org. Chem. 1998, 63, 3185-3189
3185
P a lla d iu m -Ca ta lyzed Oxid a tion of P r im a r y a n d Secon d a r y Allylic
a n d Ben zylic Alcoh ols
Karl P. Peterson and Richard C. Larock*
Department of Chemistry, Iowa State University, Ames, Iowa 50011
Received J uly 14, 1997
An efficient procedure for the oxidation of primary and secondary allylic and benzylic alcohols to
aldehydes and ketones, respectively, has been achieved using catalytic Pd(OAc)
2
in dimethyl
sulfoxide (DMSO) with oxygen gas as the sole reoxidant of the palladium. Secondary substrates
show increased reaction rates and improved yields with the addition of 2 equiv of NaHCO
reactions are free of acetal/ketal and ester byproducts.
3
. The
In tr od u ction
In 1994, Echavarren reported that the oxidation of
allylic alcohols using a catalyst system consisting of 10
The palladium-catalyzed oxidation of alcohols was
perhaps first described by Berzelius in 1828, when he
mol % Pd(PPh
3
)
6
4
in toluene in the presence or absence
and K CO at 100 °C under an O
2
of both NH PF
4
2
3
reported the reduction of most of the palladium from a
atmosphere gave moderate to good yields of the corre-
sponding R,â-unsaturated carbonyl compounds. This
1
wet ethanolic solution of K
2
PdCl
4
.
Recent efforts to
6b
make this oxidation synthetically useful have focused on
the need to make the process catalytic in palladium,
thereby requiring a means of oxidizing the reduced
palladium back to the active state. Efforts toward the
development of catalytic procedures have concentrated
system was only applied to allylic substrates. Variations
of this procedure were shown to produce diallyl ethers
as major byproducts.
2
Catalytic oxidations of alcohols using O as the ulti-
mate stoichiometric oxidant have not been limited to
palladium chemistry. Many procedures using a variety
of metals and co-oxidants have been reported. Oxygen
gas has been used as the sole reoxidant in combination
2
3
on the use of reoxidants such as metal salts, peroxides,
4
and organic halides or have used the allylic carbonate
derivative of the alcohol to be oxidized.5 The ideal
reagent for this purpose is molecular oxygen, which is
readily available, inexpensive, and nontoxic and should
produce water as the sole byproduct.
7
8
9
10
11
with Ru, Co, Cu, Pt, and Rh catalysts, and proce-
12
13
14
15
dures using Cu, Ru, Zr, and Co catalysts plus
additional co-oxidants in combination with oxygen gas
have been reported.
Procedures for the palladium-catalyzed oxidation of
alcohols using O
2
as the reoxidant have been developed,
There has also been one report of a stoichiometric
procedure for the selective oxidation of allylic alcohols
but have been limited as to the type of substrate
which can be oxidized or the need for coreagents in order
to obtain reasonable yields of the desired carbonyl
1
6
in the presence of other hydroxyl groups.
Several
products.6 The use of O
2
as the sole reoxidant of
(7) (a) Tang, R.; Diamond, S. E.; Neary, N.; Mares, F. J . Chem. Soc.,
palladium in the oxidation of alcohols was first reported
Chem. Commun. 1978, 562. (b) Matsumoto, M.; Ito, S. Synth. Commun.
1984, 14, 697-700. (c) Matsumoto, M.; Watanabe, N. J . Org. Chem.
by Schwartz in 1977.6a A catalytic system consisting of
1
984, 49, 3435-36. (d) Bilgrien, C.; Davis, S.; Drago, R. S. J . Am. Chem.
1
mol % PdCl
2
and 0.5 equiv of NaOAc in ethylene
atmosphere led to the
Soc. 1987, 109, 3786-87. (e) Mark o´ , I. E.; Giles, P. R.; Tsukazaki, M.;
Chell e´ -Regnaut, I.; Urch, C. J .; Brown, S. M. J . Am. Chem. Soc. 1997,
carbonate at 38 °C with an O
2
1
19, 12661-62.
efficient oxidation of saturated primary and second-
ary alcohols. An attempt to oxidize an olefinic alcohol
failed. This was reported to be due to poisoning of the
catalyst caused by strong complexation of palladium by
the olefin.
(
8) (a) Yamada, T.; Mukaiyama, T. Chem. Lett. 1989, 519-22. (b)
Marko, I. E.; Giles, P. R.; Tsukazaki, M.; Brown, S. M.; Urch, C. J .
Science 1996, 274, 2044-46.
(
9) (a) Driscoll, J . J .; Kosman, D. J . J . Am. Chem. Soc. 1987, 109,
1
765-72. (b) Liu, X.; Qiu, A.; Sawyer, D. T. J . Am. Chem. Soc. 1993,
115, 3239-43.
(
J ia, C.-G.; J ing, F.-Y.; Hu, W.-D.; Huang, M.-Y.; J iang, Y.-Y. J . Mol.
Catal. 1994, 91, 139-47.
(11) Martin, J .; Martin, C.; Faraj, M.; Bregeault, J . Nouv. J . Chim.
1984, 8, 141-43.
10) (a) Heyns, K.; Blazejewicz, L. Tetrahedron 1960, 9, 67-75. (b)
(
(
(
1) Berzelius, J . J . Ann. 1828, 13, 435.
2) Lloyd, W. G. J . Org. Chem. 1967, 32, 2816-19.
3) (a) Tsuji, Y.; Ohata, T.; Ido, T.; Minbu, H.; Watanabe, Y. J .
Organomet. Chem. 1984, 270, 333-41. (b) Barak, G.; Dakka, J .; Sasson,
(12) (a) Semmelhack, M. F.; Schmid, C. R.; Cortes, D. A.; Chou, C.
S. J . Am. Chem. Soc. 1984, 106, 3374-76. (b) Mark o´ , I. E.; Giles, P.
R.; Tsukazaki, M.; Brown, S. M.; Urch, C. J . Science 1996, 274, 2044.
(13) B a¨ ckvall, J . E.; Chowdhury, R. L.; Karlsson, H. J . Chem. Soc.,
Chem. Commun. 1991, 473-75. (b) Murahashi, S. I.; Naota, T.; Hirai,
J . J . Org. Chem. 1993, 58, 8, 7318-19. (c) Ley, S. V.; Norman, J .;
Griffith, W. P.; Marsden, S. P. Synthesis 1994, 639-66. (d) Murahashi,
S. I.; Naota, T.; Oda, Y.; Hirai, N. Synlett 1995, 733-34. (e) Inokuchi,
T.; Nakagawa, T.; Torii, S. Tetrahedron Lett. 1995, 36, 3223- 26.
(14) Krohn, K.; Vinke, I.; Adam, H. J . Org. Chem. 1996, 61, 1467-
72.
Y. J . Org. Chem. 1988, 53, 3553-55.
(4) (a) Tamaru, Y.; Yamamoto, Y.; Yamada, Y.; Yoshida, Z. Tetra-
hedron Lett. 1979, 16, 1401-04. (b) Tamaru, Y.; Inoue, K.; Yamada,
Y.; Yoshida, Z. Tetrahedron Lett. 1981, 22, 1801-04. (c) Tamaru, Y.;
Yamada, Y.; Inoue, K.; Yamamoto, Y.; Yoshida, Z. J . Org. Chem. 1983,
4
4
8, 1286-92. (d) Nagashima, H.; Sato, K.; Tsuji, J . Tetrahedron 1985,
1, 5645-51. (e) Choudary, B. M.; Reddy, N. P.; Kantam, M. L.; J amil,
Z. Tetrahedron Lett. 1985, 26, 6257-58. (f) A ¨ı t-Mohand, S.; H e` nin, F.;
Muzart, J . Tetrahedron Lett. 1995, 36, 2473-76.
(5) Minami, I.; Shimizu, I.; Tsuji, J . J . Organomet. Chem. 1985, 396,
2
69-80.
(15) Iwahama, T.; Sakaguchi, S.; Nishiyama, Y.; Ishii, Y. Tetrahe-
dron Lett. 1995, 36, 6923-26.
(16) Bellosta, V.; Benhaddou, R.; Czernecki, S. Synlett 1993, 861-
63.
(
6) (a) Blackburn, T. F.; Schwartz, J . J . Chem. Soc., Chem. Commun.
1
977, 157-58. (b) Gomez-Bengoa, E.; Noheda, P.; Echavarren, A. M.
Tetrahedron Lett. 1994, 35, 7097-98.
S0022-3263(97)01268-1 CCC: $15.00 © 1998 American Chemical Society
Published on Web 04/23/1998