Contribution of hyperconjugation and inductive effects to the pseudo-anomeric effect in 4-substituted methoxycyclohexanes

Bruno A. Piscelli; David O’Hagan; Rodrigo A. Cormanich

doi:10.1021/acs.jpca.2c08090

Contribution of hyperconjugation and inductive effects to the pseudo-anomeric effect in 4-substituted methoxycyclohexanes

Bruno A. Piscelli, David O’Hagan, Rodrigo A. Cormanich^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

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 σ_CH → σ_CX* hyperconjugation and the electropositive charge on 3,5-axial hydrogens (H_ax). In essence, better σ_CX* (or π_CO*) acceptors increase the charge on 3,5-CH_ax, which in turn strengthens C^δ+H_ax···^δ−OMe NCHB interactions.

Original language	English
Pages (from-to)	724–728
Number of pages	5
Journal	Journal of Physical Chemistry A
Volume	127
Issue number	3
Early online date	17 Jan 2023
DOIs	https://doi.org/10.1021/acs.jpca.2c08090
Publication status	Published - 26 Jan 2023

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title = "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.",

author = "Piscelli, {Bruno A.} and David O{\textquoteright}Hagan and Cormanich, {Rodrigo A.}",

note = "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).",

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T1 - Contribution of hyperconjugation and inductive effects to the pseudo-anomeric effect in 4-substituted methoxycyclohexanes

AU - Piscelli, Bruno A.

AU - O’Hagan, David

AU - Cormanich, Rodrigo A.

N1 - 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).

PY - 2023/1/26

Y1 - 2023/1/26

N2 - 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.

AB - 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.

U2 - 10.1021/acs.jpca.2c08090

DO - 10.1021/acs.jpca.2c08090

M3 - Article

SN - 1089-5639

VL - 127

SP - 724

EP - 728

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 3

ER -

Contribution of hyperconjugation and inductive effects to the pseudo-anomeric effect in 4-substituted methoxycyclohexanes

Abstract

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