C-F Bonds as "Frozen" Nucleophiles: Unconsummated SN2 Reactions

J Org Chem. 2022 Oct 7;87(19):13406-13410. doi: 10.1021/acs.joc.2c01788. Epub 2022 Sep 27.

Abstract

In this note, we present a series of rigid molecules that show close enforced interactions between Ar-F moieties and -CH2X groups in a "tetrel bond" configuration similar to a nascent SN2 attack. We explore the spectroscopic, crystallographic, and chemical reactivity consequences of these unusual interactions, including significant through-space spin-spin couplings, short C-F···CH2X distances, and differential SN1 and SN2 reaction pathways. We also reveal experimental evidence of carbon-based tetrel bonds influencing chemical reactivity in solution. Finally, density functional theory (DFT) calculations are employed throughout this study to confirm and illuminate our experimental data.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Carbon*

Substances

  • Carbon