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

被引：8

作者：

Genaev, Alexander M. ^{[1
]}

Shchegoleva, Lyudmila N. ^{[1
]}

Salnikov, George E. ^{[1
,2
,3
]}

Shernyukov, Andrey V. ^{[1
,2
]}

Shundrin, Leonid A. ^{[1
,2
]}

Shundrina, Inna K. ^{[1
,2
]}

Zhu, Zhongwei ^{[2
]}

Koltunov, Konstantin Yu. ^{[2
,4
]}

机构：

[1] NN Vorozhtsov Novosibirsk Inst Organ Chem, Pr Akad Lavrentieva 9, Novosibirsk 630090, Russia

[2] Novosibirsk State Univ, Pirogova 2, Novosibirsk 630090, Russia

[3] Int Tomog Ctr, Inst Skaya 3a, Novosibirsk 630090, Russia

[4] Boreskov Inst Catalysis, Pr Akad Lavrentieva 5, Novosibirsk 630090, Russia

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2019年 / 84卷 / 11期

关键词：

HYDROGEN-TRANSFER; BINOL; THERMOLYSIS; EFFICIENT; RADICALS;

D O I：

10.1021/acs.joc.9b00915

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Experiments show that 1,1'-bi-2-naphthol (BINOL) undergoes facile C1-C1' bond cleavage under action of triflic acid at temperatures above 0 degrees 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 intermediary of its neutral diketo form.

引用

页码：7238 / 7243

页数：6

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