Preparation, X-ray Structure, and Reactivity of Triisopropylsilyl-Substituted Aryliodonium Salts

Mekhman S. Yusubov, Dmitrii Yu Svitich, Akira Yoshimura, Brent J. Kastern, Victor N. Nemykin, Viktor Vladimirovich Zhdankin

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

(4-Triisopropylsilylphenyl)phenyliodonium tosylate, an aryliodonium salt bearing an extremely bulky, electron-donating triisopropylsilyl (TIPS) substituent in the phenyl ring, was prepared by the reaction of (4-tributyltinphenyl)triisopropylsilane with [hydroxy(tosyloxy)iodo]benzene (Koser's reagent). The TIPS-substituted aryliodonium tosylate was further converted into (4-triisopropylsilylphenyl)phenyliodonium bromide, the structure of which was established by single-crystal X-ray diffraction. Reactions of the TIPS-substituted arylodonium tosylate with bromide, azide, and thiocyanate anions predominantly afforded products of nucleophilic substitution in the electron-rich aromatic ring bearing the TIPS substituent. This unusual result is explained by the steric effect of the extraordinary bulky para-TIPS substituent on the configuration of the reaction intermediate.

Original languageEnglish
Pages (from-to)4831-4834
Number of pages4
JournalEuropean Journal of Organic Chemistry
Volume2015
Issue number22
DOIs
Publication statusPublished - 1 Aug 2015

Fingerprint

Bearings (structural)
Bromides
bromides
reactivity
Salts
salts
X rays
Reaction intermediates
preparation
reaction intermediates
Azides
Electrons
rings
Anions
reagents
electrons
x rays
Substitution reactions
benzene
Single crystals

Keywords

  • Hypervalent compounds
  • Iodine
  • Silicon
  • Steric hindrance

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Preparation, X-ray Structure, and Reactivity of Triisopropylsilyl-Substituted Aryliodonium Salts. / Yusubov, Mekhman S.; Svitich, Dmitrii Yu; Yoshimura, Akira; Kastern, Brent J.; Nemykin, Victor N.; Zhdankin, Viktor Vladimirovich.

In: European Journal of Organic Chemistry, Vol. 2015, No. 22, 01.08.2015, p. 4831-4834.

Research output: Contribution to journalArticle

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AU - Nemykin, Victor N.

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KW - Steric hindrance

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