title: Anomalous stereoselectivity in the Wittig reaction: the role of steric interactions.
abstract: Density functional theory calculations combined with a distortion/interaction energy analysis show that the anomalous Z selectivity observed in Wittig reactions of ortho-substituted benzaldehydes is not caused by phosphorus-heteroatom interactions in the addition transition state, as assumed in earlier work, but is predominantly steric in nature. The calculations reproduced correctly the stereoselectivity preferences for a wide range of reactant pairs as well as relative reactivities for different substituent types, providing deeper structural insight into the mechanism of Wittig olefination.
authors.affiliation: Wydział Chemii, Uniwersytet Wrocławski , ul. F. Joliot-Curie 14, 50-383 Wrocław, Poland.
authors.forename: Marcin
authors.initials: M
authors.lastname: Stępień
mesh_terms: D001547:Benzaldehydes / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D011789:Quantum Theory; D013237:Stereoisomerism
chemical_list: D001547:Benzaldehydes