Acylzirconocene chloride: Formation of carbocycles by palladium-catalyzed cascade reaction |
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Authors: | Yuji Hanzawa Yusuke Oka |
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Affiliation: | a Laboratory of Organic Reaction Chemistry, Showa Pharmaceutical University, 3-3165 Higashi-Tamagawagakuen, Machida, Tokyo 194-8543, Japan b Tokyo University of Pharmacy and Life Science, 1432-1 Hachioji, Horinouchi, Tokyo 192-0392, Japan |
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Abstract: | Acylzirconocene chloride complex as an acyl group donor reacts with ω-carbonyl α,β-enones or with bis-enones to give carbocyclic compounds under 10 mol% Pd(OAc)2-catalyzed conditions, and each reaction was accelerated by the addition of a stoichiometric amount of Me2Zn. The formation of the carbocycles from ω-carbonyl α,β-enones was considered to be a result of a series of reactions; (i) the formation of Pd(II)-intermediate by an electron transfer from the Pd(0)-catalyst to an α,β-enone function in an initial step, (ii) an acyl group transfer from the acylzirconocene complex to the Pd(II)-intermediate (transmetalation), (iii) the reductive elimination of Pd(0)-metal, and (iv) an intramolecular addition of metal enolate to ω-carbonyl group. On the other hand, the reaction of bis-enones with acylzirconocene chloride under the identical condition afforded reductive cyclization product, bicyclo[3.3.0] octane derivatives, in which acyl group from acylzirconocene complex was not incorporated. |
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Keywords: | Acylzirconocene chloride Palladium catalyst Cascade reaction Reductive cyclization |
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