Journal of the American Chemical Society
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a
Conditions: N-nitrosoaniline (1 equiv), alkyne (1.5 equiv), CH3CN
b
c
(2 mL). Isolated yields. The structure of the alkyne substrate is in
the parentheses.
CONCLUSION
■
In summary, a C−H activation-based intermolecular redox-
neutral strategy for indole synthesis has been developed. Our
N−N bond-based internal oxidant approach offers a valuable
complement to the thus far exclusively used N−O variant for
the synthesis of azaheterocycles. The compatibility of seemingly
dichotomous acidic and basic conditions as well as tolerance of
an array of auxiliary functional groups ensures reaction
versatility and structure tunability for multifarious synthetic
contexts. Comprehensive mechanistic studies, under acidic
condition, support [RhCp*]2+ as generally the catalyst resting
state (switchable to [RhCp*(OOCtBu)]+ under certain
circumstance) and C−H activation as the turnover-limiting
step. Given the diversity of accessible covalent linkages for the
nitroso group, this labile functionality is likely to serve as a
generic synthetic handle for strikingly diverse coupling
reactions.
́
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ASSOCIATED CONTENT
* Supporting Information
Synthetic procedures, mechanistic studies, and NMR data. This
material is available free of charge via the Internet at http://
■
S
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AUTHOR INFORMATION
Corresponding Author
Notes
■
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
J.Z. gratefully acknowledges support from the National Natural
Science Foundation of China (21274058) and the National
Basic Research Program of China (2013CB922101,
2011CB935801).
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