Acid-Catalyzed Versus Thermally Induced C1–C1′ Bond Cleavage in 1,1′-Bi-2-naphthol: An Experimental and Theoretical Study | Sciact - CRIS-system of Boreskov Institute of Catalysis

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 , E-ISSN: 1520-6904

Output data

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

Tags

Chemistry; Organic compounds

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	N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Pr. Akademika Lavrentieva 9, Novosibirsk 630090, Russia
2	Novosibirsk State University, Pirogova 2, Novosibirsk 630090, Russia
3	International Tomography Center, Institutskaya 3a, Novosibirsk 630090, Russia
4	Boreskov Institute of Catalysis, Pr. Akademika Lavrentieva 5, Novosibirsk 630090, Russia

Funding (1)

Russian Foundation for Basic Research

17-03-00564 (АААА-А17-117040310053-5)

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.

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 AN PMID OpenAlex

Submitted:	Apr 3, 2019
Published online:	May 14, 2019
Published print:	Jun 7, 2019

Web of science:	WOS:000471212000063
Scopus:	2-s2.0-85066959293
Elibrary:	41647947
Chemical Abstracts:	2019:936838
PMID:	31083942
OpenAlex:	W2946321888

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