title: Origin of the E/Z Selectivity in the Synthesis of Tetrasubstituted Olefins by Wittig Reaction of α-Fluorophosphonium Ylides: An Explanation for the Low Stereoselectivity Observed in Reactions of α-Alkoxy Aldehydes.
abstract: A series of tetrasubstituted fluoroalkenes were synthesized in good yield and high E/Z selectivity (up to 96/4) by Wittig reaction between α-heterosubstituted ketones and α-fluorophosphonium ylides. A detailed study of factors that control stereoselectivity in these reactions shows that stereoselectivity is the result of stabilizing CH···F and N···C═O interactions in the addition TS leading to the E isomer. This analysis provides a rationale for the observed decrease in selectivity for reactions of stabilized ylides with α-alkoxy aldehydes.
authors.affiliation: Janssen Pharmaceutical Companies of Johnson & Johnson, API Small Molecule Development, Turnhoutseweg 30, 2340 Beerse, Belgium.
authors.forename: Dominique
authors.identifier: 0000-0001-6718-085X
authors.initials: D
authors.lastname: Depré
authors.affiliation: Janssen Pharmaceutical Companies of Johnson & Johnson, API Small Molecule Development, Turnhoutseweg 30, 2340 Beerse, Belgium.
authors.forename: Wim A A
authors.initials: WA
authors.lastname: Vermeulen
authors.affiliation: Janssen Pharmaceutical Companies of Johnson & Johnson, API Small Molecule Development, Turnhoutseweg 30, 2340 Beerse, Belgium.
authors.forename: Yolande
authors.initials: Y
authors.lastname: Lang
authors.affiliation: Janssen Pharmaceutical Companies of Johnson & Johnson, API Small Molecule Development, Turnhoutseweg 30, 2340 Beerse, Belgium.
authors.forename: Jean
authors.initials: J
authors.lastname: Dubois
authors.affiliation: Janssen Pharmaceutical Companies of Johnson & Johnson, API Small Molecule Development, Turnhoutseweg 30, 2340 Beerse, Belgium.
authors.forename: Jan
authors.initials: J
authors.lastname: Vandevivere
authors.affiliation: Janssen Pharmaceutical Companies of Johnson & Johnson, API Small Molecule Development, Turnhoutseweg 30, 2340 Beerse, Belgium.
authors.forename: Jeremy
authors.initials: J
authors.lastname: Vandermeersch
authors.affiliation: Janssen Pharmaceutical Companies of Johnson & Johnson, API Small Molecule Development, Turnhoutseweg 30, 2340 Beerse, Belgium.
authors.forename: Longchuan
authors.initials: L
authors.lastname: Huang
authors.affiliation: Institute of Condensed Matter and Nanosciences, Université catholique de Louvain , Place Louis Pasteur 1, Box L4.01.02, 1348 Louvain-la-Neuve, Belgium.
authors.forename: Raphaël
authors.identifier: 0000-0002-3449-565X
authors.initials: R
authors.lastname: Robiette