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Updated: Aug 14, 2025

Efficient Synthesis of All-Carbon Quaternary Centers via the Conjugate Addition of Functionalized Monoorganozinc Bromides
Published on: May 26, 2019
Contribution of Hyperconjugation and Inductive Effects to the Pseudo-anomeric Effect in 4-Substituted
Bruno A Piscelli1, David O'Hagan2, Rodrigo A Cormanich1
1Chemistry Institute, University of Campinas, Monteiro Lobato Street, Campinas 13083-862, Sao Paulo, Brazil.
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.
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