6-Aryl-5,6-dihydrodibenzo[c,e][1,2]azaborinines display restricted rotation at the boron-carbon aryl bond, yielding conformational isomers or atropisomers. The stereodynamic processes were monitored by variable-temperature NMR (D-NMR), dynamic enantioselective HPLC (D-HPLC), or kinetic racemization measurements. The absolute configuration of stable atropisomers (compound 1d, ΔGrac = 26.0 kcal·mol-1) was determined by TD-DFT simulation of the electronic circular dichroism (ECD) spectra. The racemization energy of 1d is more than 12 kcal·mol-1 smaller than its isostere 9-(2-methylnaphthalen-1-yl)phenanthrene.
Mazzanti A., Boffa M., Marotta E., Mancinelli M. (2019). Axial Chirality at the Boron-Carbon Bond: Synthesis, Stereodynamic Analysis, and Atropisomeric Resolution of 6-Aryl-5,6-dihydrodibenzo[ c,e][1,2]azaborinines. JOURNAL OF ORGANIC CHEMISTRY, 84(19), 12253-12258 [10.1021/acs.joc.9b01550].
Axial Chirality at the Boron-Carbon Bond: Synthesis, Stereodynamic Analysis, and Atropisomeric Resolution of 6-Aryl-5,6-dihydrodibenzo[ c,e][1,2]azaborinines
Mazzanti A.;Marotta E.;Mancinelli M.
2019
Abstract
6-Aryl-5,6-dihydrodibenzo[c,e][1,2]azaborinines display restricted rotation at the boron-carbon aryl bond, yielding conformational isomers or atropisomers. The stereodynamic processes were monitored by variable-temperature NMR (D-NMR), dynamic enantioselective HPLC (D-HPLC), or kinetic racemization measurements. The absolute configuration of stable atropisomers (compound 1d, ΔGrac = 26.0 kcal·mol-1) was determined by TD-DFT simulation of the electronic circular dichroism (ECD) spectra. The racemization energy of 1d is more than 12 kcal·mol-1 smaller than its isostere 9-(2-methylnaphthalen-1-yl)phenanthrene.File | Dimensione | Formato | |
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