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Solvent and temperature effect in aldol condensation between the lithium enolate of tert-butyl acetate and 2-phenyl propanal: enthalpy and entropy contribution

✍ Scribed by Gianfranco Cainelli; Paola Galletti; Daria Giacomini; Paolo Orioli


Book ID
104231376
Publisher
Elsevier Science
Year
2001
Tongue
French
Weight
65 KB
Volume
42
Category
Article
ISSN
0040-4039

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✦ Synopsis


An analysis of nucleophilic addition of the lithium enolate of tert-butyl acetate and 2-phenyl propanal in two different solvents, such as THF and n-hexane, revealed the great importance of solvent effect in determining the stereoselectivity. In particular, temperature-dependent measurements of diastereomeric ratio allow the evaluation of diastereoselectivity in terms of differential enthalpy and entropy of activation for this reaction. Either in THF or n-hexane we obtained a predominance of the anti isomer in all temperature ranges, but in THF the diastereoselection is controlled by the differential activation enthalpy, whereas in n-hexane it is the sole differential activation entropy that accounts for the anti predominance.