A. Genaev, L. Shchegoleva, G. E. Salnikov
May 14, 2019
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Influential Citations
7
Citations
Journal
The Journal of organic chemistry
Abstract
Experiments show that 1,1'-bi-2-naphthol (BINOL) undergoes facile C1-C1' bond cleavage under action of triflic acid at temperatures above 0 °C to give mainly 2-naphthol along with oligomeric material. CASSCF and MRMP//CASSCF computations have demonstrated unambiguously that this unusual mode of scission of the biaryl bond can occur in the C1,C1'-diprotonated form of BINOL via a mechanism involving homolytic cleavage prompted by the intramolecular electrostatic repulsion. These findings also provide insights into the mechanism of a comparatively easy thermal cleavage of BINOL, implying the intermediacy of its neutral diketo form.