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Arylation with Unsymmetrical Diaryliodonium Salts: A Chemoselectivity Study
Author(s) -
Malmgren Joel,
Santoro Stefano,
Jalalian Nazli,
Himo Fahmi,
Olofsson Berit
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201300860
Subject(s) - chemoselectivity , aryl , moiety , chemistry , nucleophile , catalysis , combinatorial chemistry , reagent , thio , substrate (aquarium) , organic chemistry , alkyl , oceanography , geology
Phenols, anilines, and malonates have been arylated under metal‐free conditions with twelve aryl(phenyl)iodonium salts in a systematic chemoselectivity study. A new “ anti‐ortho effect” has been identified in the arylation of malonates. Several “dummy groups” have been found that give complete chemoselectivity in the transfer of the phenyl moiety, irrespective of the nucleophile. An aryl exchange in the diaryliodonium salts has been observed under certain arylation conditions. DFT calculations have been performed to investigate the reaction mechanism and to elucidate the origins of the observed selectivities. These results are expected to facilitate the design of chiral diaryliodonium salts and the development of catalytic arylation reactions that are based on these sustainable and metal‐free reagents.