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

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
* Author to whom correspondence should be addressed.
Received: 2 June 2004; in revised form: 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

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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.

AMA Style

Nudelman NS, Vázquez A. Solvent and Ligand Effects on the Tandem Addition-Lithiation-Electrophilic Substitution of Phenyllithium on α,β-Unsaturated Carbonyl Compounds. International Journal of Molecular Sciences. 2005; 6(1):97-103.

Chicago/Turabian Style

Nudelman, N. S.; Vázquez, Alvaro. 2005. "Solvent and Ligand Effects on the Tandem Addition-Lithiation-Electrophilic Substitution of Phenyllithium on α,β-Unsaturated Carbonyl Compounds." Int. J. Mol. Sci. 6, no. 1: 97-103.

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