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Synthesis of Polysubstituted Iodoarenes Enabled by Iterative Iodine‐Directed para and ortho C−H Functionalization
Author(s) -
Wu Yichen,
Bouvet Sébastien,
Izquierdo Susana,
Shafir Alexandr
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201809657
Subject(s) - halogen , surface modification , silanes , iodine , chemistry , halogenation , allylic rearrangement , combinatorial chemistry , sulfonyl , organic chemistry , catalysis , alkyl , silane
Among halogenated aromatics, iodoarenes are unique in their ability to produce the bench‐stable halogen(III) form. Earlier, such iodine(III) centers were shown to enable C−H functionalization ortho to iodine via halogen‐centered rearrangement. The broader implications of this phenomenon are explored by testing the extent of an unusual iodane‐directed para C−H benzylation, as well as by developing an efficient C−H coupling with sulfonyl‐substituted allylic silanes. Through the combination of the one‐shot nature of the coupling event and the iodine retention, multisubstituted arenes can be prepared by sequentially engaging up to three aromatic C−H sites. This type of iodine‐based iterative synthesis will serve as a tool for the formation of value‐added aromatic cores.