106989-32-6Relevant academic research and scientific papers
Stereolabile and configurationally stable atropisomers of hindered aryl carbinols
Casarini, Daniele,Coluccini, Carmine,Lunazzi, Lodovico,Mazzanti, Andrea
, p. 5098 - 5102 (2005)
Carbinols of the Ar-C(OH)R2 type, Ar being o-isopropylphenyl, exist as stereolabile syn-clinal (sc) and anti-periplanar (ap) atropisomers when R = Me, Et, i-Pr. In the latter compound, the major atropisomer also comprises two enantiomeric forms that interchange with a barrier of 6.4 kcal mol -1. X-ray diffraction, NOE experiments, and ab initio calculations indicate that the sc-atropisomer is the more stable form when R = Me, i-Pr, t-Bu but is the less stable one when R = Et. NMR spectra at variable temperature allowed the determination of the barriers for the interconversion of the sc- into the ap-atropisomers (ΔG? = 7.6, 8.8, and 13.5 kcal mol -1 for Me, Et, i-Pr, respectively). When R is a tert-butyl group, the two atropisomers are configurationally stable: the ap-atropisomer is obtained as the kinetic controlled compound, which can be transformed into the thermodynamically more stable sc-atropisomer with a free energy of activation of 29.3 kcal mol-1. Both atropisomers exhibit restricted rotation of the tert-butyl moiety, the corresponding ΔG? values being 9.4 and 8.8 kcal mol-1 for the sc- and ap-atropisomer, respectively.
Highly active chiral ruthenium catalysts for asymmetric ring-closing olefin metathesis
Funk, Timothy W.,Berlin, Jacob M.,Grubbs, Robert H.
, p. 1840 - 1846 (2007/10/03)
The synthesis of olefin metathesis catalysts containing chiral, monodentate N-heterocyclic carbenes and their application to asymmetric ring-closing metathesis (ARCM) are reported. These catalysts retain the high levels of reactivity found in the related
