Computational evidence that hyperconjugative interactions are not responsible for the anomeric effect.

Nature Chemistry
Yirong Mo

Abstract

The 'anomeric effect' is the thermodynamic preference for polar substituents to occupy the axial position in the chair conformation of various heterocycles. The most common explanation given for this effect at present is hyperconjugation from the lone pairs on the ring heteroatom to the antibonding orbital between the anomeric carbon and its linking substituent. Alternatively, the anomeric effect could be explained by intramolecular electrostatic interactions between local dipoles. Few models can provide convincing data for either theory at the quantum-mechanical level. Now, using the extended block-localized wavefunction method, which is the simplest form of valence bond theory, we have evaluated the degree of hyperconjugation in various compounds that display the anomeric effect and have interpreted their conformational preferences in terms of steric, hyperconjugation and dispersion effects. The results provide strong evidence that hyperconjugative interactions are not responsible for the anomeric effect and that it is better interpreted in terms of electrostatic interactions.

References

Sep 23, 2003·Angewandte Chemie·F Matthias Bickelhaupt, Evert Jan Baerends
Feb 11, 2005·Journal of Computational Chemistry·Lingchun SongWei Wu
Feb 17, 2006·The Journal of Physical Chemistry. a·Mathieu LinaresStéphane Humbel
Feb 21, 2007·Accounts of Chemical Research·Yirong Mo, Jiali Gao
Mar 3, 2007·Journal of Computational Chemistry·Antonio Vila, Ricardo A Mosquera
Jul 28, 2007·The Journal of Physical Chemistry. a·Yirong MoYuchun Lin
Aug 7, 2009·Chemistry : a European Journal·Annika Bande, Josef Michl

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Citations

May 15, 2012·The Journal of Physical Chemistry. B·Benedict M SattelleAndrew Almond
Sep 27, 2012·The Journal of Physical Chemistry. a·Jean C SummertonMichael S Chapman
Mar 4, 2011·Physical Chemistry Chemical Physics : PCCP·Yirong MoJiali Gao
Mar 3, 2011·The Journal of Chemical Physics·Ying HuangShubin Liu
Jan 16, 2016·The Journal of Organic Chemistry·Eusebio Juaristi, Rafael Notario
Feb 19, 2016·The Journal of Physical Chemistry Letters·Elena R AlonsoJosé L Alonso
May 4, 2016·Chemistry : a European Journal·Huaiyu ZhangYirong Mo
Sep 26, 2015·Physical Chemistry Chemical Physics : PCCP·David Ferro-Costas, Ricardo A Mosquera
May 30, 2015·Organic & Biomolecular Chemistry·Neda HasanzadehBahareh Ahmadi
Mar 15, 2018·Physical Chemistry Chemical Physics : PCCP·C FraschettiA Filippi
Aug 25, 2015·Physical Chemistry Chemical Physics : PCCP·Masato MoritaKaito Takahashi
Dec 12, 2012·Chemistry : a European Journal·Changwei WangYirong Mo
Jun 11, 2014·Journal of Molecular Modeling·Judy I-Chia WuYirong Mo
Jun 5, 2012·Chemical Society Reviews·Jérôme F GonthierClémence Corminboeuf
Dec 15, 2015·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Pilar Gema Rodríguez OrtegaJuan Jesus Lopez Gonzalez
Oct 26, 2016·ChemistryOpen·Rituparna Das, Balaram Mukhopadhyay
Mar 22, 2013·Organic & Biomolecular Chemistry·Matheus P Freitas
Jan 7, 2011·Nature·Emilio J CocineroBenjamin G Davis
Jul 31, 2013·Journal of Computational Chemistry·Laetitia BombleClemence Corminboeuf
Jun 16, 2012·Physical Chemistry Chemical Physics : PCCP·Balazs PinterFrank De Proft
Feb 18, 2012·Organic & Biomolecular Chemistry·Ian Cumpstey
Jul 22, 2014·Angewandte Chemie·Bixue XuMatthieu Sollogoub
May 1, 2020·European Journal of Organic Chemistry·Shyam S Samanta, Stéphane P Roche
Nov 23, 2012·Organic & Biomolecular Chemistry·Glauco F BauerfeldtClarissa O da Silva
Sep 10, 2020·Chemistry : a European Journal·Rachel Hevey
Jan 12, 2021·Organic & Biomolecular Chemistry·Constantinos A TsipisJohn K Gallos
Feb 17, 2021·The Journal of Organic Chemistry·Samuel C BrydonJonathan M White
Mar 11, 2021·Physical Chemistry Chemical Physics : PCCP·Bruno A PiscelliRodrigo A Cormanich
Oct 30, 2010·The Journal of Physical Chemistry. B·Carol A DeakyneJoel F Liebman
Feb 17, 2011·The Journal of Physical Chemistry. a·Antonio VilaRicardo A Mosquera
May 12, 2011·The Journal of Physical Chemistry. a·Stephan N SteinmannYirong Mo
Aug 11, 2012·The Journal of Organic Chemistry·Matheus P Freitas

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