Acid-Catalyzed Versus Thermally Induced C1-C1′ Bond Cleavage in 1,1′-Bi-2-naphthol: An Experimental and Theoretical Study

Alexander M. Genaev, Lyudmila N. Shchegoleva, George E. Salnikov, Andrey V. Shernyukov, Leonid A. Shundrin, Inna K. Shundrina, Zhongwei Zhu, Konstantin Yu Koltunov

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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.

Original languageEnglish
Pages (from-to)7238-7243
Number of pages6
JournalJournal of Organic Chemistry
Volume84
Issue number11
DOIs
Publication statusPublished - 7 Jun 2019

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Keywords

  • HYDROGEN-TRANSFER
  • BINOL
  • THERMOLYSIS
  • EFFICIENT
  • RADICALS

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