Asymmetric nucleophilic monofluorobenzylation of allyl and propargyl halides mediated by a remote sulfinyl group: synthesis of homoallylic and homopropargylic fluorides

Yolanda Arroyo; M Ascensión Sanz-Tejedor; Alejandro Parra; Inés Alonso; José Luis García Ruano

doi:10.1021/jo501096f

Asymmetric nucleophilic monofluorobenzylation of allyl and propargyl halides mediated by a remote sulfinyl group: synthesis of homoallylic and homopropargylic fluorides

J Org Chem. 2014 Aug 1;79(15):6970-7. doi: 10.1021/jo501096f. Epub 2014 Jul 14.

Authors

Yolanda Arroyo¹, M Ascensión Sanz-Tejedor, Alejandro Parra, Inés Alonso, José Luis García Ruano

Affiliation

¹ Departamento de Química Orgánica (EII), Universidad de Valladolid , Paseo del Cauce 59, 47011 Valladolid, Spain.

PMID: 24977923
DOI: 10.1021/jo501096f

Abstract

Fluorinated 2-(p-tolylsulfinyl)benzyl carbanions react with allyl and propargyl halides in a highly stereoselective way, providing homoallylic and homopropargylic fluorides, respectively, with high optical purity. Theoretical calculations found transition states for these transformations whose relative stabilities are consistent with the experimentally observed stereoselectivity.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Anions / chemistry*
Benzyl Compounds / chemistry*
Fluorides / chemistry*
Hydrocarbons, Fluorinated / chemical synthesis*
Hydrocarbons, Fluorinated / chemistry*
Magnetic Resonance Spectroscopy
Molecular Structure
Pargyline / analogs & derivatives
Pargyline / chemical synthesis*
Pargyline / chemistry*
Quantum Theory
Stereoisomerism

Substances

Anions
Benzyl Compounds
Hydrocarbons, Fluorinated
Pargyline
Fluorides