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(Reference retrieved automatically from Web of Science through information on FAPESP grant and its corresponding number as mentioned in the publication by the authors.)

Fluorine-Induced Pseudo-Anomeric Effects in Methoxycyclohexanes through Electrostatic 1,3-Diaxial Interactions

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Author(s):
Piscelli, Bruno A. [1] ; Sanders, William [2] ; Yu, Cihang [2] ; Al Maharik, Nawaf [2, 3] ; Lebl, Thomas [2] ; Cormanich, Rodrigo A. [1] ; O'Hagan, David [2]
Total Authors: 7
Affiliation:
[1] Univ Estadual Campinas, Chem Inst, Monteiro Lobato St, BR-13083862 Campinas, SP - Brazil
[2] Univ St Andrews, Sch Chem, St Andrews KY16 9ST, Fife - Scotland
[3] An Najah Natl Univ, Fac Sci, Dept Chem, POB 7, Nabulus, West Bank - Palestine
Total Affiliations: 3
Document type: Journal article
Source: CHEMISTRY-A EUROPEAN JOURNAL; v. 26, n. 52 AUG 2020.
Web of Science Citations: 0
Abstract

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 hydrogen atoms electropositive. The electrostatic interaction between these axial hydrogen atoms 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 (F-19[H-1]-NMR at -80 degrees C) 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. (AU)

FAPESP's process: 18/03910-1 - Physicochemical studies of fluorinated organic compounds: experimental and theoretical approaches
Grantee:Rodrigo Antonio Cormanich
Support Opportunities: Research Grants - Young Investigators Grants
FAPESP's process: 19/05028-7 - Physico-chemical studies of organofluorine compounds: experimental and theoretical approaches
Grantee:Rodrigo Antonio Cormanich
Support Opportunities: Research Grants - Visiting Researcher Grant - International
FAPESP's process: 19/03855-3 - Synthesis of fluorinated derivatives of thymol and carvacrol and study of their physico-chemical properties
Grantee:Bruno de Almeida Piscelli
Support Opportunities: Scholarships in Brazil - Scientific Initiation