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Solvation of the Carbonyl Compound as a Predominant Factor in the Diastereofacial Selectivity of Nucleophilic Addition
Author(s) -
Cainelli Gianfranco,
Galletti Paola,
Giacomini Daria,
Orioli Paolo
Publication year - 2000
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/(sici)1521-3773(20000204)39:3<523::aid-anie523>3.0.co;2-b
Subject(s) - nucleophile , solvation , chemistry , selectivity , solvent , aldehyde , nucleophilic addition , butyllithium , medicinal chemistry , computational chemistry , organic chemistry , catalysis
Temperature‐dependent selectivity in nucleophilic additions is affected by the solvent. The inversion temperature (marked with arrows in the graph) that appears in the nonlinear Eyring plots of ln ( anti/syn ) versus temperature for the addition of butyllithium to an O‐protected α ‐hydroxy aldehyde 1 does not depend on nucleophiles ( n BuLi (▴), t BuLi (•)), but on the solvent. Its value can be obtained from a plot of the 13 C NMR chemical shift of C=O versus temperature. TBDMS= t BuMe 2 Si.