2018
DOI: 10.1021/acs.accounts.8b00192
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Informing Molecular Design by Stereoelectronic Theory: The Fluorine Gauche Effect in Catalysis

Abstract: The axioms of stereoelectronic theory constitute an atlas to navigate the contours of molecular space. All too rarely lauded, the advent and development of stereoelectronic theory has been one of organic chemistry's greatest triumphs. Inevitably, however, in the absence of a comprehensive treatise, many of the field's pioneers do not receive the veneration that they merit. Rather their legacies are the stereoelectronic pillars that persist in teaching and research. This ubiquity continues to afford practitione… Show more

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Cited by 109 publications
(46 citation statements)
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References 100 publications
(151 reference statements)
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“…In contrast, a mismatch of the proline stereochemistry and the observed conformation at proline leads to protein destabilization. In addition, 4‐substituted prolines have been incorporated in pharmaceuticals and within asymmetric catalysts …”
Section: Resultssupporting
confidence: 89%
“…In contrast, a mismatch of the proline stereochemistry and the observed conformation at proline leads to protein destabilization. In addition, 4‐substituted prolines have been incorporated in pharmaceuticals and within asymmetric catalysts …”
Section: Resultssupporting
confidence: 89%
“…The fluorine gauche effect starts to find interesting application of in catalysis and control of organic reactivity …”
Section: Spectroscopic Signatures Of Hyperconjugationmentioning
confidence: 99%
“…Remarkably, in 5 a the fluorine atoms are located trans to the OH groups without any gauche conformation. The preference for trans disposition over classical gauche stabilization is of utmost importance and in contradiction with common observations on 1,2‐fluorohydrins . This effect can be explained through stabilization of the linear structure by triol H‐bonding, which probably minimizes dipole–dipole interactions.…”
Section: Structure Aggregation and Organogelation Of Triolsmentioning
confidence: 69%
“…Often relying on fluorinated aromatics or perfluorinated chains, the positive effect of fluorine insertion has also been used with success in materials sciences . The electronic modulation and conformational restriction through the so‐called gauche effect developed in drug design are also useful for the design of improved catalysts …”
Section: Introductionmentioning
confidence: 99%