: We report counter intuitive axial preferences in non stereochemically biased, selectively fluorinated methoxycyclohexanes. These pseudo-anomeric effects are apparent when electronegative CF2 groups are placed at the C-2, C-4 and C-6 positions of the cyclohexane ring to render the C-3/5 axial hydrogens electropositive. The electrostatic interaction between these axial hydrogens and the -OMe oxygen is stabilising. The effect is explored using high level ab initio and DFT calculations in the framework of NBO, QTAIM and NCI analysis across a range of derivatives, and experimentally ( 19F{1H}-NMR at -80oC) for some illustrative examples. The effect is significant in energy terms for a weak interaction, and illustrates a new stereoelectronic aspect attributed to selective fluorine substitution in organic chemistry

Title

Chemistry - A European Journal

Publisher

Wihly

Publisher Country

Germany

Indexing

Scopus

Impact Factor

5.236

Publication Type

Both (Printed and Online)

Volume

16

Year

2020

Pages

11989-11994