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C−H Functionalization—Prediction of Selectivity in Iridium(I)‐Catalyzed Hydrogen Isotope Exchange Competition Reactions
Author(s) -
Valero Mégane,
Kruissink Thomas,
Blass Jennifer,
Weck Remo,
Güssregen Stefan,
Plowright Alleyn T.,
Derdau Volker
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201914220
Subject(s) - iridium , imes , catalysis , chemistry , selectivity , reactivity (psychology) , competition (biology) , substrate (aquarium) , medicinal chemistry , photochemistry , combinatorial chemistry , organic chemistry , carbene , medicine , ecology , oceanography , alternative medicine , pathology , biology , geology
An assessment of the C−H activation catalyst [(COD)Ir(IMes)(PPh 3 )]PF 6 (COD=1,5‐cyclooctadiene, IMes=1,3‐bis(2,4,6‐trimethylphenyl)imidazol‐2‐ylidene) in the deuteration of phenyl rings containing different functional directing groups is divulged. Competition experiments have revealed a clear order of the directing groups in the hydrogen isotope exchange (HIE) with an iridium (I) catalyst. Through DFT calculations the iridium–substrate coordination complex has been identified to be the main trigger for reactivity and selectivity in the competition situation with two or more directing groups. We postulate that the competition concept found in this HIE reaction can be used to explain regioselectivities in other transition‐metal‐catalyzed functionalization reactions of complex drug‐type molecules as long as a C−H activation mechanism is involved.