Catalytic intermolecular hydroaminations of unactivated olefins with secondary alkyl amines

Andrew J. Musacchio, Brendan C. Lainhart, Xin Zhang, Saeed G. Naguib, Trevor C. Sherwood, Robert R. Knowles

Research output: Contribution to journalArticle

107 Scopus citations

Abstract

The intermolecular hydroamination of unactivated alkenes with simple dialkyl amines remains an unsolved problem in organic synthesis. We report a catalytic protocol for efficient additions of cyclic and acyclic secondary alkyl amines to a wide range of alkyl olefins with complete anti-Markovnikov regioselectivity. In this process, carbon-nitrogen bond formation proceeds through a key aminium radical cation intermediate that is generated via electron transfer between an excited-state iridium photocatalyst and an amine substrate. These reactions are redox-neutral and completely atom-economical, exhibit broad functional group tolerance, and occur readily at room temperature under visible light irradiation. Certain tertiary amine products generated through this method are formally endergonic relative to their constituent olefin and amine starting materials and thus are not accessible via direct coupling with conventional ground-state catalysts.

Original languageEnglish (US)
Pages (from-to)727-730
Number of pages4
JournalScience
Volume355
Issue number6326
DOIs
StatePublished - Feb 17 2017

All Science Journal Classification (ASJC) codes

  • General

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    Musacchio, A. J., Lainhart, B. C., Zhang, X., Naguib, S. G., Sherwood, T. C., & Knowles, R. R. (2017). Catalytic intermolecular hydroaminations of unactivated olefins with secondary alkyl amines. Science, 355(6326), 727-730. https://doi.org/10.1126/science.aal3010