jo016397m_si_001.pdf (116.6 kB)
Conformational Studies by Dynamic NMR. 86. Structure, Stereodynamics, and Cryogenic Enantioseparation of the Stereolabile Isomers of o-Dinaphthylphenyl Derivatives
journal contribution
posted on 2002-02-06, 00:00 authored by Carlo Dell'Erba, Francesco Gasparrini, Stefano Grilli, Lodovico Lunazzi, Andrea Mazzanti, Marino Novi, Marco Pierini, Cinzia Tavani, Claudio VillaniStatic and dynamic stereochemistry of the hydrocarbon comprising a phenyl ring bearing two
α-naphthyl substituents in the ortho positions, i.e., 1,2-di-(4-methyl-naphth-1-yl)-benzene 1, has
been studied by a combination of variable temperature NMR, cryogenic HPLC, and MM calculations.
Whereas in solution both syn (meso) and anti (chiral) forms were observed and the corresponding
interconversion barrier was determined (ΔG⧧ = 19.5 kcal mol-1), only the diastereoisomer anti
was found to be present in the crystalline state (X-ray diffraction). When the molecule is rendered
asymmetric by introduction of a nitro group in the phenyl ring as in 1,2-di-(4-methyl-naphth-1-yl)-4-nitrobenzene 2, the chiral syn and anti diastereoisomers are simultaneously present both in
solution and in the solid state, albeit in different proportions. Cryogenic chromatography on a HPLC
chiral stationary phase at −20 °C allowed the stereolabile diastereoisomers and the corresponding
enantiomers to be separated.