Contribution of hyperconjugation and inductive effects to the pseudo-anomeric effect in 4-substituted methoxycyclohexanes
Abstract
The importance of electrostatic nonconventional hydrogen bonds (NCHBs) to the pseudo-anomeric effect of 4-substituted methoxycyclohexanes is evaluated using theory [natural bond orbital (NBO)] to deconvolute electrostatic from other contributing effects. There is an interesting interplay between σCH → σCX* hyperconjugation and the electropositive charge on 3,5-axial hydrogens (Hax). In essence, better σCX* (or πCO*) acceptors increase the charge on 3,5-CHax, which in turn strengthens Cδ+Hax···δ−OMe NCHB interactions.
Citation
Piscelli , B A , O’Hagan , D & Cormanich , R A 2023 , ' Contribution of hyperconjugation and inductive effects to the pseudo -anomeric effect in 4-substituted methoxycyclohexanes ' , Journal of Physical Chemistry A , vol. 127 , no. 3 , pp. 724–728 . https://doi.org/10.1021/acs.jpca.2c08090
Publication
Journal of Physical Chemistry A
Status
Peer reviewed
ISSN
1089-5639Type
Journal article
Description
Funding: We gratefully acknowledge FAPESP for a PhD scholarship to B.A.P. (#2021/09716-5) and a Young Research Award to R.A.C. (#2018/03910-1) and FAEPEX for a fellowship (2479/21).Collections
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