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

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

Journal

Journal of Organic Chemistry
ISSN: 0022-3263

Output data

Year: 2019, Volume: 84, Number: 11, Pages: 7238-7243 Pages count : 6 DOI: 10.1021/acs.joc.9b00915

Authors

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

Affiliations

1	(Данные Web of science) NN Vorozhtsov Novosibirsk Inst Organ Chem, Pr Akad Lavrentieva 9, Novosibirsk 630090, Russia
2	(Данные Web of science) Novosibirsk State Univ, Pirogova 2, Novosibirsk 630090, Russia
3	(Данные Web of science) Int Tomog Ctr, Inst Skaya 3a, Novosibirsk 630090, Russia
4	(Данные Web of science) Boreskov Inst Catalysis, Pr Akad Lavrentieva 5, Novosibirsk 630090, Russia

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.

Genaev A.M. , Shchegoleva L.N. , Salnikov G.E. , Shernyukov A.V. , Shundrin L.A. , Shundrina I.K. , Zhu Z. , Koltunov K.Y.
Acid-Catalyzed Versus Thermally Induced C1-C1 ' Bond Cleavage in 1,1 '-Bi-2-naphthol: An Experimental and Theoretical Study
Journal of Organic Chemistry. 2019. V.84. N11. P.7238-7243. DOI: 10.1021/acs.joc.9b00915 WOS Scopus РИНЦ OpenAlex

Published online:	May 14, 2019
Published print:	Jun 7, 2019

Web of science:	WOS:000471212000063
Scopus:	2-s2.0-85066959293
Elibrary:	41647947
OpenAlex:	W2946321888

DB	Citing
Web of science	8
Scopus	10
Elibrary	7
OpenAlex	10