Stereoelectronic substituent effects

Accounts of Chemical Research
Henrik Helligsø Jensen, Mikael Bols

Abstract

An investigation was carried out on the influence of the stereochemistry of substituents, particularly hydroxyl groups, on their electronic effects in piperidines, carbohydrates (pyranosides), and related compounds. Polar groups, such as OH, OR, and F, were found in the 3 and 4 position to be much more electron-withdrawing when positioned equatorially rather than axially. In contrast, little difference in electronic effects was observed from apolar groups as a result of epimerization. These observations were believed to be caused by differences in charge-dipole interactions and were used to explain why stereoisomeric glycosides hydrolyze with different rates. The conformational changes of hydroxylated piperidines and related compounds as a function of pH were likewise explained from the different substituent effects of axial and equatorial OH groups.

References

Sep 30, 2004·Journal of the American Chemical Society·Ciaran McDonnellMikael Bols
Apr 14, 2005·Organic & Biomolecular Chemistry·Anette GregersenMikael Bols

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Citations

Jun 6, 2008·Journal of Medicinal Chemistry·Aiming SunJames P Snyder
Mar 23, 2007·The Journal of Organic Chemistry·David Crich, Olga Vinogradova
Apr 15, 2010·The Journal of Organic Chemistry·Matthew SchombsJacquelyn Gervay-Hague
Feb 18, 2010·Nature Chemistry·Thomas J BoltjeGeert-Jan Boons
May 21, 2008·Chemical Communications : Chem Comm·Christian Marcus PedersenMikael Bols
Oct 10, 2009·The Journal of Organic Chemistry·Jennifer R KrumperK A Woerpel
May 26, 2016·The Journal of Organic Chemistry·Mads HeuckendorffHenrik H Jensen
Sep 21, 2016·The Journal of Organic Chemistry·Akihiro ImamuraMakoto Kiso
Jul 1, 2012·Wiley Interdisciplinary Reviews. Computational Molecular Science·B Lachele FoleyRobert J Woods
Feb 8, 2014·Organic Letters·Mads HeuckendorffMikael Bols
Jan 27, 2017·Chemical Communications : Chem Comm·K Kowalska, C M Pedersen
Mar 4, 2017·Chembiochem : a European Journal of Chemical Biology·Erwin R van RijsselJeroen D C Codée
Mar 14, 2018·Organic & Biomolecular Chemistry·Lulu Teressa PoulsenHenrik H Jensen
May 5, 2011·Chemistry : a European Journal·Christian M PedersenMikael Bols
Aug 21, 2007·Chemistry : a European Journal·Henrik H JensenMikael Bols
Sep 20, 2008·Organic & Biomolecular Chemistry·Helle ChristensenHenrik Helligsø Jensen
Jan 29, 2009·Angewandte Chemie·Xiangming Zhu, Richard R Schmidt
Dec 7, 2010·Chemistry : a European Journal·Mads HeuckendorffMikael Bols
Jan 22, 2010·Organic & Biomolecular Chemistry·Laurel K Mydock, Alexei V Demchenko
Feb 24, 2017·Beilstein Journal of Organic Chemistry·Mikael Bols, Christian Marcus Pedersen
Feb 2, 2017·Beilstein Journal of Organic Chemistry·Felicia D'AndreaVenerando Pistarà
Mar 8, 2013·ChemMedChem·Suazette Reid MooringHyunsuk Shim
Feb 7, 2012·Chemical Communications : Chem Comm·Alphert E ChristinaJeroen D C Codée
Sep 5, 2008·Chemistry : a European Journal·Jasper DinkelaarGijsbert A van der Marel
Dec 7, 2018·Journal of Carbohydrate Chemistry·Crystal L O'NeilAlexei V Demchenko
Mar 20, 2019·The Journal of Antibiotics·Simon S Park, Jacquelyn Gervay-Hague
Dec 15, 2020·Chemistry : a European Journal·Debashis Dhara, Laurence A Mulard
Mar 12, 2021·The Journal of Organic Chemistry·Martin KurfiřtJindřich Karban
Nov 4, 2008·Journal of the American Chemical Society·Torsten LinkerMichael Schmittel
Mar 16, 2007·Organic Letters·Yasunori OkadaHidetoshi Yamada

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