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Int. J. Mol. Sci. 2005, 6(1), 97-103; doi:10.3390/i6010097

Solvent and Ligand Effects on the Tandem Addition-Lithiation-Electrophilic Substitution of Phenyllithium on α,β-Unsaturated Carbonyl Compounds

Department of Organic Chemistry, Facultad de Ciencias Exactas, Universidad de Buenos Aires. Pab. II, P. 3, Ciudad Universitaria, 1428 Buenos Aires, Argentina
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Received: 2 June 2004 / Revised: 15 June 2004 / Accepted: 17 December 2004 / Published: 31 January 2005
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Abstract

The reaction of phenyllithium with E-cinnamaldehyde is extremely sensitive to the reaction conditions and surprising changes in the product distribution were observed upon changes in the solvent, concentrations, duration or temperature of the reaction. For these reasons the above mentioned reaction was considered an appropriate model to examine solvent and aggregation effects of PhLi. On the other hand, when two or trhee equiv of phenyllithium are used, instead of one, the reaction transforms into a surprising tandem addition-lithiation-β-alkylation sequence, that can be successfully applied to the synthesis of substituted dihydrochalcones. The observed effects upon changes in the reaction conditions, as well as the effects of additives that modify the PhLi dimer-monomer equilibrium are consistent with a reaction pathway in which dimeric phenyl lithium attacks to the E-cinnamaldehyde without previous deaggregation. Usually, monomers are found to be more reactive than dimers, but, in this reaction the opposite effect is observed, and the tandem reaction spectacularly decreases with the (PhLi)2 concentration.
Keywords: Phenyllithium; tandem reactions; aggregates; cinnamaldehyde; chalcones Phenyllithium; tandem reactions; aggregates; cinnamaldehyde; chalcones
This is an open access article distributed under the Creative Commons Attribution License (CC BY 3.0).

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MDPI and ACS Style

Nudelman, N.S.; Vázquez, A. Solvent and Ligand Effects on the Tandem Addition-Lithiation-Electrophilic Substitution of Phenyllithium on α,β-Unsaturated Carbonyl Compounds. Int. J. Mol. Sci. 2005, 6, 97-103.

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