Structure, Conformation, and Stereodynamics of the Atropisomers of Highly Hindered Benzyl Ethers
2006-06-09T00:00:00Z (GMT) by
Low-temperature and NOE NMR spectra of four of the title compounds indicate that they adopt a synclinal (sc) conformation, in agreement with the prediction of ab initio computations. In the case of the most-hindered derivative (compound <b>4</b>), the conformation is syn-periplanar (sp), as is also shown by X-ray diffraction. Such stereolabile sp- or sc-atropisomers exist as two conformational enantiomers: the corresponding enantiomerization barriers, covering the range 6.6 to 9.7 kcal mol<sup>-1</sup>, could be measured for all the examined compounds. In two cases (compounds <b>3</b> and <b>5</b>), the minor antiperiplanar (ap) atropisomer has been also observed, and the sc to ap interconversion barrier measured (11.7 and 11.9 kcal mol<sup>-1</sup>, respectively). In addition, restricted rotation of the isopropyl and <i>tert</i>-butyl substituents has been detected, and the corresponding barriers have been determined.
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