Highly Selective C–F Bond Functionalization of Tetrasubstituted <i>gem</i>-Difluoroalkenes and Trisubstituted Monofluoroalkenes Using Grignard Reagents
Yanhui Wang, Yihan Tang, Yuwei Zong, Gavin Chit Tsui
Abstract
We herein describe selective C–F bond functionalizations of tetrasubstituted gem-difluoroalkenes and trisubstituted monofluoroalkenes using Grignard reagents without the transition metal catalyst. β,β-Difluoroacrylates react with Grignard reagents under mild conditions to afford tetrasubstituted (E)-β-monofluoroacrylates. Experimental and computational studies revealed that the selectivity stems from the intrinsic reactivity difference between the (E)- and (Z)-isomers toward excess Grignard reagent, which leads to the resolution of the two products.
Topics & Concepts
ChemistryReagentReactivity (psychology)Grignard reagentCombinatorial chemistrySurface modificationSelectivityCatalysisMedicinal chemistryOrganic chemistryPathologyPhysical chemistryAlternative medicineMedicineFluorine in Organic ChemistryCyclopropane Reaction MechanismsCarbohydrate Chemistry and Synthesis