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Scheme 5. Proposed Reaction Mechanism
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from the oxidation of NHC−AuCl with Selectfluor. The
coordination of the triple bond of enynone 1 to [Au] enhanced
the electrophilicity of the alkyne, and the subsequent intra-
molecular nucleophilic attack of the carbonyl oxygen atom to the
electron-deficient alkyne would form the intermediate B. In the
presence of alkenes or X−H, the carbene intermediate was then
trapped to form the cyclopropanes 3 or insertion products 6.
In conclusion, we have found that the combination of NHC−
gold complex and Selectfluor is a highly efficient catalyst system
for carbene-transfer reactions, with the TON up to 990000 and
the TOF up to 82500 h−1. The reaction probably proceeded
through a cationic Au(III)+ species, which was generated in situ
from the oxidation of NHC−AuCl with Selectfluor. Further
investigations of the detailed reaction mechanism and
application of this system are currently underway in our
laboratory.
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ASSOCIATED CONTENT
* Supporting Information
■
S
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(d) Fianchini, M.; Dai, H.; Dias, H. V. R. Chem. Commun. 2009,
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M. J. Inorganic Synthesis; Wiley: New York, 2007; Vol. 27, pp 218−221.
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Typical experimental procedure and characterization for all
products. This material is available free of charge via the Internet
AUTHOR INFORMATION
Corresponding Author
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We are grateful to the National Basic Research Program of China
(973) (2011CB808600) and NNSFC (21172077, 21372086),
Guangdong NSF (103510641 01000000), SRF for ROCS, State
Education Ministry, and “The Fundamental Research Funds for
the Central Universities, SCUT”.
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(b) Eberhard, M. R. Org. Lett. 2004, 6, 2125. (c) Pad, C.; Hartman, W.
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