Dynamic Cross‐Exchange in Halophosphonium Species: Direct Observation of Stereochemical Inversion in the Course of an SN2 Process. Issue 6 (6th December 2017)

• Record Type: Journal Article
• Authors: Nikitin, Kirill; Jennings, Elizabeth V.; Al Sulaimi, Sulaiman; Ortin, Yannick; Gilheany, Declan G.
• Is Part Of: Angewandte Chemie international edition. Volume 57:Issue 6(2018)
• Page Start: 1480
• Page End: 1484
• Publication Date: 2017-12-06
• Subjects: configuration inversion -- NMR spectroscopy -- nucleophilic substitution -- phosphorus -- stereogenic compounds; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201708649
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The complex fluxional interconversions between otherwise very similar phosphonium bromides and chlorides R3 PX + X − (R=Alk, Ar, X=Cl or Br) were studied by NMR techniques. Their energy barriers are typically ca. 11 kcal mol −1, but rise rapidly as bulky groups are attached to phosphorus, revealing the importance of steric factors. In contrast, electronic effects, as measured by Hammett analysis, are modest ( ρ 1.46) but still clearly indicate negative charge flow towards phosphorus in the transition state. Most significantly, detailed analysis of the exchange pathways unequivocally, and for the first time in any such process, shows that nucleophilic attack of the nucleophilic anion on the tetrahedral centre results in inversion of configuration. Abstract : Double lift : The energy barrier to halogen exchange in halophosphonium species rises rapidly when either bulky substituents or electron‐donating groups are present. When degeneracy is lifted twice (see picture), measurement of diastereomeric cross‐exchange provides direct observation of stereochemical inversion in the course of an SN 2 process.