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Preparation, X‐ray Structure, and Reactivity of Triisopropylsilyl‐Substituted Aryliodonium Salts
Author(s) -
Yusubov Mekhman S.,
Svitich Dmitrii Yu.,
Yoshimura Akira,
Kastern Brent J.,
Nemykin Victor N.,
Zhdankin Viktor V.
Publication year - 2015
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201500535
Subject(s) - chemistry , substituent , bromide , medicinal chemistry , aryl , steric effects , ring (chemistry) , reactivity (psychology) , nucleophile , tetrafluoroborate , reagent , thiocyanate , nucleophilic substitution , stereochemistry , organic chemistry , alkyl , ionic liquid , catalysis , medicine , alternative medicine , pathology
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.