Iridium-Catalyzed, Intermolecular Hydroamination of Unactivated Alkenes with Indoles

The addition of an N–H bond to an olefin is the most direct route for the synthesis of alkylamines. Currently, intermolecular hydroamination is limited to reactions of a narrow range of reagents containing N–H bonds or activated alkenes, and all the examples of additions to unactivated alkenes requi...

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Published inJournal of the American Chemical Society Vol. 136; no. 8; pp. 3200 - 3207
Main Authors Sevov, Christo S, Zhou, Jianrong (Steve), Hartwig, John F
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 26.02.2014
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Multidisciplinary
Physical Sciences
Science & Technology
RHODIUM
MIGRATORY INSERTION
C-N
ALKYLATION
VINYLARENES
ASYMMETRIC HYDROAMINATION
INTRAMOLECULAR HYDROAMINATION
ENANTIOSELECTIVE HYDROAMINATION
BOND FORMATION
OLEFINS
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Summary:The addition of an N–H bond to an olefin is the most direct route for the synthesis of alkylamines. Currently, intermolecular hydroamination is limited to reactions of a narrow range of reagents containing N–H bonds or activated alkenes, and all the examples of additions to unactivated alkenes require large excesses of alkene. We report intermolecular hydroamination reactions of indoles with unactivated olefins. The reactions occur with as few as 1.5 equiv of olefin to form N-alkylindoles exclusively and in good yield. Characterizations of the catalyst resting state, kinetic data, labeling studies, and computational data imply that the addition occurs by olefin insertion into the Ir–N bond of an N-indolyl complex and that this insertion reaction is faster than insertion of olefin into the Ir–C bond of the isomeric C-2-indolyl complex.
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ISSN:0002-7863
1520-5126
DOI:10.1021/ja412116d