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Catalytic intermolecular hydroaminations of unactivated olefins with secondary alkyl amines

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Science  17 Feb 2017:
Vol. 355, Issue 6326, pp. 727-730
DOI: 10.1126/science.aal3010

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Hydroamination gets a light push uphill

Hydroamination of olefins is a broadly useful method for making carbon-nitrogen bonds. However, when both the amine and the olefin have multiple alkyl substituents, the reaction can become energetically unfavorable. Musacchio et al. used the energy in blue light to surmount this obstacle (see the Perspective by Buchanan and Hull). A photo-excited iridium complex oxidized the amine, which in turn bonded efficiently to the olefin, after which a thiophenol cocatalyst shuttled the electron back. The reaction could operate across a wide range of amine and olefin partners.

Science, this issue p. 727; see also p. 690

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.

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