30262-98-7Relevant articles and documents
A new reaction between E-cinnamaldehyde and phenyllithium. Mechanistic studies
Nudelman, Norma S.,Schulz, Hernan G.
, p. 2761 - 2767 (1999)
The reaction of phenyllithium (in excess) with E-cinnamaldehyde gives a surprising tandem addition β-alkylation, which can be successfully used for the synthesis of substituted dihydrochalcones. The mechanism by which these unexpected reactions could occur is unknown and experimental and theoretical studies were carried out as a contribution to its understanding. The observed concentration effects, the surprising changes in the product distribution upon changes in the reaction conditions, the haptomeric structure of the calculated intermediates and the calculated activation energies are consistent with a reaction pathway in which dimeric phenyllithium attacks the E-cinnamaldehyde without prior deaggregation. Solvated structures were also calculated using a "dielectric continuum" model for solvent effects.
Tandem addition β-lithiation - Alkylation sequence on α,β-unsaturated aldehydes
Nudelman,Garcia
, p. 1387 - 1394 (2007/10/03)
A tandem reaction between (E)-cinnamaldehyde, 1a, and phenyllithium affording β-substituted dihydrochalcones was recently reported. NMR spectroscopic studies on the reaction mixture, as well as isotopic exchange reactions and trapping of two intermediates, provide clues on the several mechanistic steps of this new reaction. Extended studies revealed that β-alkyl-substituted α,β-unsaturated aldehydes and aliphatic lithium reagents did not afford good yields of the tandem reaction products, while aromatic lithium reagents gave good results. The aggregation features of the aryllithium reagents and the extended charged delocalization effects are considered to promote β-selectivity. This approach provides a convenient route for the synthesis of a wide variety of β-alkyl-substituted dihydrochalcones.
Synthesis of β-silylated olefins from α,β-unsaturated aldehydes and ketones
Bolourtchian,Mojtahedi,Saidi
, p. 590 - 591 (2007/10/03)
α,β-Unsaturated aldehydes and ketones such as phorone, benzalacetone, benzalacetophenone, 4-(2-furyl)-3-buten-4-one and β-ionone, react with TMS-Cl in the presence of Li in THF to give conjugated β-silylated enoxysilanes. Hydrolysis of this compounds in a
