Abstract
The oxidation of terminal olefins with palladium salts usually affords methyl ketones.1–3 However, in 1986 it was reported that aldehydes could be obtained using a catalyst comprising (CH3CN)2Pd(NO2)Cl and CuCl2 in t-butanol solvent, which was proposed to be bimetallic with the NO2 group intact.4 Our studies suggest that this catalyst is best described as a Wacker-like oxidation catalyst modified by an alkyl nitrite, and we report an improved version of this catalyst. Moreover, the application of our system to the oxidation of terminal olefins with allylic substituents has led to some insight as to the potential role of the copper co-catalyst in Wacker-like reactions.
IR data (THF-d8): Nitrate bands: 1549, 1500, 1300, 1288, 1255 cm-1. Nitrosyl band: 1860 cm-1. The nitrosyl compound could be independently generated by treating CuCl2 with NOC1 in THF. This nitrosyl complex is rapidly converted to the mixture of nitrate species on exposure to oxygen.
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References
P.M. Maitlis. “The Organic Chemistry of Palladium,” vol. 2, Academic, New York (1971).
P.M. Henry. “Palladium Catalyzed Oxidation of Hydrocarbons,” D. Reidel, Dordrecht (1980).
J. Tsuji. “Organic Synthesis with Palladium Compounds,” Springer-Verlag, New York (1980).
J.-y. Lai, X.-x. Shi, L.-x. Dai, J. Org. Chem.. 57:3485 (1992).
T. Hosokawa, Y. Ataka, S.-I. Murahashi, Bull. Chem. Soc. Jpn. 63:166 (1990).
T. Hosokawa, T. Shinohara, Y. Ooka, S.-I. Murahashi, Chem. Lett. 2001 (1989).
J. Nogami, H. Ogawa, S. Miyamoto, T. Mandai, S. Wakabayashi, J. Tsuji, Tetrahedron Lett. 29:5181 (1988).
A.K. Base, L. Krishnan, D.R. Wagle, M.S. Menhas, Tetrahedron Lett. 27:5955 (1986).
T. Hosokawa, T. Ohta, S.-I. Murahashi, J. Chem. Soc., Chem. Commun. 848 (1983).
E.C. Alyea, S.A. Dias, G. Ferguson, A.J. McAlees, R. McCrindle, P.J. Roberts, J. Am. Chem. Soc. 99:4985 (1977).
W.G. Lloyd, B.J. Luberoff, J. Org. Chem. 34:3949 (1969).
A 65% aldehyde selectivity for the oxidation of allyl acetate in the presence of hexamethylphosphoric triamide has also been reported: T. Hosokawa, S. Aoki, M. Takano, T. Nakahira, Y. Yoshida, S.-I. Murahashi, J. Chem. Soc., Chem. Commun. 1559 (1991).
B.L. Feringa, J. Chem. Soc., Chem. Commun. ,909 (1986).
M.A. Andrews and K.P. Kelly, J. Am. Chem. Soc. 103:2894 (1981).
M.A. Andrews and C.-W.F. Cheng, J. Am. Chem. Soc. 104:4268(1982).
M.A. Andrews, T.C.-T. Chang, C.-W.F. Cheng, T.J. Emge, K.P. Kelly, and T.F. Koetzle, J. Am. Chem. Soc. 106:5913 (1984).
M.A. Andrews, T.C.-T. Chang, C.-W.F. Cheng, and K.P. Kelly, Organometallics 3:1777 (1984).
M.A. Andrews, T.C.-T. Chang, and C.-W.F. Cheng, Organometallics 4:268 (1985).
T.T. Wenzel, J. Chem. Soc., Chem. Commun. 932 (1989).
I.I. Moiseev, A. A. Grigor’ev, S.V. Pestrikov, Zh. Org. Khim.. 4:354 (1968).
P.M. Henry. “Palladium Catalyzed Oxidation of Hydrocarbons,” p. 133, D. Reidel, Dordrecht (1980).
P.M. Henry. “Palladium Catalyzed Oxidation of Hydrocarbons,” p 43, D. Reidel, Dordrecht (1980).
T. Hosokawa, S.-I. Murahashi, Acc. Chem. Res. 23:49 (1990) and references cited therein.
Cu(II)-O-O-Cu(II) species: (see, for instance, Z. Tyeklar, K.D. Karlin, Acc. Chem. Res. ,22:241 (1989)
Cu(III)-O species: (see, for instance, N. Kitajima, T. Koda, Y. Iwata, Y. Moro-oka, J. Am. Chem. Soc. 112:8833 (1990).
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Wenzel, T.T. (1993). Oxidation of Olefins to Aldehydes Using a Palladium-Copper Catalyst. In: Barton, D.H.R., Martell, A.E., Sawyer, D.T. (eds) The Activation of Dioxygen and Homogeneous Catalytic Oxidation. Springer, Boston, MA. https://doi.org/10.1007/978-1-4615-3000-8_9
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DOI: https://doi.org/10.1007/978-1-4615-3000-8_9
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