Acid-Catalyzed Versus Thermally Induced C1-C1' Bond Cleavage in 1,1'-Bi-2-naphthol: An Experimental and Theoretical Study
Genaev, AM; Shchegoleva, LN; Salnikov, GE; Shernyukov, AV; Shundrin, LA; Shundrina, IK; Zhu, Z; Koltunov, KY
| HERO ID | 5416781 |
|---|---|
| In Press | No |
| Year | 2019 |
| Title | Acid-Catalyzed Versus Thermally Induced C1-C1' Bond Cleavage in 1,1'-Bi-2-naphthol: An Experimental and Theoretical Study |
| Authors | Genaev, AM; Shchegoleva, LN; Salnikov, GE; Shernyukov, AV; Shundrin, LA; Shundrina, IK; Zhu, Z; Koltunov, KY |
| Journal | Journal of Organic Chemistry |
| Volume | 84 |
| Issue | 11 |
| Page Numbers | 7238-7243 |
| 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. |
| Doi | 10.1021/acs.joc.9b00915 |
| Pmid | 31083942 |
| Is Certified Translation | No |
| Dupe Override | No |
| Is Public | Yes |
| Language Text | English |