Reactions of 1-arylbenziodoxolones with azide anion: Experimental and computational study of substituent effects

Yusubov, Mekhman, Soldatova, Natalia, Postnikov, Pavel, Valiev, Rashid, Svitich, Dmitry, Yusubova, Roza, Yoshimura, Akira, Wirth, Thomas ORCID: https://orcid.org/0000-0002-8990-0667 and Zhdankin, Viktor 2018. Reactions of 1-arylbenziodoxolones with azide anion: Experimental and computational study of substituent effects. European Journal of Organic Chemistry 2018 (5) , pp. 640-647. 10.1002/ejoc.201701595

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Abstract

New substituted 1-arylbenziodoxolones were prepared and their reactivity with azide anion nucleophile was investigated. It was found that independent on the presence of substituents, all reactions of 1-arylbenziodoxolones proceed as nucleophilic substitution of the iodonium leaving group in the electron-deficient benziodoxolone benzene ring. The presence of bulky substituents in the ortho-position of the aryl ring slowers the reaction, while the presence of a moderately electron-withdrawing bromine substituent in the para-position to iodine in the benziodoxolone ring moderately increases the rate of substitution. The presence of a strongly electron-withdrawing nitro group in the para-position to iodine in the benziodoxolone ring dramatically increases the rate of substitution. These observations are in agreement with the electronic requirements for internal nucleophilic substitution in the benziodoxole ring. A quantum-chemical computational study of the possible reaction paths is in agreement with the observed effects of substituents on the reactivity of arylbenziodoxolones in this reaction.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Publisher:	Wiley
ISSN:	1434-193X
Date of First Compliant Deposit:	10 January 2018
Date of Acceptance:	3 January 2018
Last Modified:	30 Nov 2024 04:45
URI:	https://orca.cardiff.ac.uk/id/eprint/108045

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