Organic Letters
Letter
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both cycles: 2 equiv of alkyne was used to build a
cyclopentenone backbone and 1 equiv of alkyne was for the
reaction of regeneration of rhodium hydride A via path II.23
In conclusion, we have developed an intermolecular [2 + 2 +
1] carbonylative cycloaddition of simple alkynes in the presence
of an alcohol, InCl3, and an [Rh(COD)Cl]2/DPEPhos catalytic
system. The alcohol plays an important role in the formation of
cyclopentenones by acting as the source of CO and facilitating
the Rh−hydride intermediate. In these transformations, alkynes
act as both the olefin and the alkyne partner in the Pauson−
Khand-type reaction. It is likely that the reaction proceeds via a
π-allylalkyne rhodium intermediate. A deeper understanding of
these reactions and their application toward organic synthesis,
as well as a comprehensive theoretical study on the mechanistic
details, are underway in our laboratory.
ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
Experimental procedure, characterization and NMR
Single-crystal X-ray diffraction data for compound 3g
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11905.
AUTHOR INFORMATION
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Corresponding Author
ORCID
(16) (a) Shibata, T.; Toshida, N.; Takagi, K. J. Org. Chem. 2002, 67,
7446−7450. (b) Morimoto, T.; Kakiuchi, K. Angew. Chem., Int. Ed.
2004, 43, 5580−5588. (c) Morimoto, T.; Fuji, K.; Tsutsumi, K.;
Kakiuchi, K. J. Am. Chem. Soc. 2002, 124, 3806−3807.
(17) Park, J. H.; Cho, Y.; Chung, Y. K. Angew. Chem., Int. Ed. 2010,
49, 5138−5141.
Notes
The authors declare no competing financial interest.
(18) Park, J. H.; Kim, S. M.; Chung, Y. K. Chem. - Eur. J. 2011, 17,
10852−10856.
ACKNOWLEDGMENTS
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(19) (a) Hoshimoto, Y.; Ohata, T.; Sasaoka, Y.; Ohashi, M.; Ogoshi,
S. J. Am. Chem. Soc. 2014, 136, 15877−15880. (b) Miura, H.;
Takeuchi, K.; Shishido, T. Angew. Chem., Int. Ed. 2016, 55, 278−282.
(20) (a) Gellrich, U.; Meißner, A.; Steffani, A.; Kahny, M.; Drexler,
H.-J.; Heller, D.; Plattner, D. A.; Breit, B. J. Am. Chem. Soc. 2014, 136,
1097−1104. (b) Phadke, N.; Findlater, M. Molecules 2015, 20, 20195−
20205.
This work was supported by a National Research Foundation of
Korea (NRF) grant funded by the Korean government
(2014R1A5A1011165 and 2007-0093864). J.H.K. and T.S.
are recipients of a BK21 Plus fellowship.
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