Stereodynamics and edge-to-face CH-pi aromatic interactions in o-phenethyl-substituted biaryls

The Journal of Organic Chemistry
W Brian JenningsJohn F Malone

Abstract

As part of a search for systems that exhibit intramolecular aromatic edge-to-face interactions, a series of four biaryl compounds containing a phenethyl side chain were prepared. These compounds exist as a slowly interconverting mixture of two atropisomers due to steric hindrance to rotation about the biaryl bond. The more thermodynamically stable isomer exhibits an abnormal shielding of an ortho-proton in solution indicative of an edge-to-face CH-pi interaction with the terminal phenyl ring on the side chain. This tilted-T type of geometry was observed in the X-ray crystal structure of one of the compounds. The edge-to-face conformation in solution is estimated by variable temperature NMR studies to be energetically favored by ca. 1.6 kcal mol(-1) but entropically disfavored by ca. 5.0 cal K(-1) mol(-1).

References

Mar 31, 2004·The Journal of Organic Chemistry·Michael S LeonardMadeleine M Joullié
Nov 20, 2004·Chemistry : a European Journal·Nikolay G LukyanenkoMark M Botoshansky

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Citations

Nov 8, 2011·Acta Crystallographica. Section E, Structure Reports Online·Gabriella OronaRalph Isovitsch
Dec 22, 2009·Organic & Biomolecular Chemistry·W Brian JenningsJohn F Malone
Jan 25, 2017·Organic & Biomolecular Chemistry·M Eugenia González-RosendeJohn F Malone
Sep 1, 2009·Chemistry : a European Journal·Simon JanichErnst-Ulrich Würthwein
Feb 12, 2009·Journal of the American Chemical Society·Alfonso MarescaClaudiu T Supuran
Jun 3, 2008·The Journal of Physical Chemistry. B·Antoni SegadeDolores Velasco
Jan 31, 2015·Journal of the American Chemical Society·Salvador Pérez-EstradaMiguel A Garcia-Garibay

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