Journal of the American Chemical Society
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vinylhydroxylamine substrate 1. The ensuing homolytic cleavage
of N−O bond in activated 1 give rise to Oꢀradical I and Nꢀradical
II, respectively. Subsequently, the emerging electrophilic Nꢀ
radical selectively engages electronꢀrich alkene 2a to afford a
secondary alkyl radical III. Consequently, this nucleophilic
radical intermediate is disposed undergo further radical addition
to substrate 1, which is comparatively electronꢀdeficient. The
following βꢀfragmentation of N−O bond in intermediate IV
delivered the desired carboamination product 4 while regenerating
Nꢀradical II to enable a chain sustention process. Taken together,
radical polar effect likely plays a central role in dictating the
selectivity of the reaction.
1
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4
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Scheme 3. Proposed reaction mechanism
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In summary, using Oꢀvinylhydroxylamine derivatives as both
the Nꢀ and Cꢀdonors under visibleꢀlightꢀsensitization,
intermolecular carboamination of unactivated alkenes was
successfully accomplished. The polarity effect underpins the
exquisite regiochemical control of this process, affording linear
products exclusively. In addition, this atom economical reaction
features mild reaction conditions, broad scope, and high
chemoselectivity. This reaction not only provides an alternative
strategy for alkeneꢀcarboamination, but also enables the
application of GTRA reactions to incorporate both carbon and
nitrogen groups onto olefins, which proves to be elusive until the
present report.
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ASSOCIATED CONTENT
This material is available free of charge via the Internet at
(13) Cai, S.ꢀH.; Xie, J.ꢀH.; Song, S.; Ye, L.; Feng, C.; Loh, T.ꢀP. ACS
Catal. 2016, 6, 5571.
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(15) A DFT calculation of the triplet energy of substrate 1j was
conducted and the obtained ET1j (calc) = 60.1 Kcal/mol is within the range
that should be accessed using [Ir(dF(CF3)ppy)2(bpy)](PF6) as a triplet
sensitizer (ET = 60.4 Kcal/mol). See SI for details.
(16) The cross over experiment of 1a, 1h and 2a suggested the
intermolecular delivery of Nꢀ and Cꢀdonors for this carboamination
reaction. See SI for details.
AUTHOR INFORMATION
Corresponding Author
*iamcfeng@njtech.edu.cn
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
We gratefully acknowledge the financial support of the
“Thousand Talents Plan” Youth Program, the “Jiangsu Speciallyꢀ
Appointed Professor Plan”, the Natural Science Foundation of
Jiangsu Province (BK20170984), and SICAM Fellowship by
Jiangsu National Synergetic Innovation Center for Advanced
Materials. We are grateful to Dr. Ming Yan for helpful discussion,
Prof. Genping Huang (Tianjin University) for the calculation of
triplet energy, Prof. Jin Xie (Nanjing University) for suggestion in
quantum yield determination.
REFERENCES
(1) (a) Patai, S. The Chemistry of Alkenes (Wiley Interscience, 1964).
(b) McDonald, R. I.; Liu, G.; Stahl, S. S. Chem. Rev. 2011, 111, 2981.
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