Organic Letters
Letter
(4) Imada, Y.; Yuasa, M.; Nakamura, I.; Murahashi, S.-I. J. Org. Chem.
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In summary, we have developed a diastereo- and
enantioselective propargylation reaction of 2-substituted
benzofuran-3(2H)-ones catalyzed by a copper-pybox complex.
A series of 2,2-disubstituted benzofuran-3(2H)-ones bearing
two vicinal chiral centers and one terminal alkyne function were
obtained in good to excellent yields and ee’s in most cases. The
utility of this method was demonstrated by a relatively large
scale synthesis of 3a and further transformation of 3a into
ketone 4 without loss of enantiomeric purity. Furthermore, this
methodology was found to be also applicable to indanone- and
benzopyranone-based substrates.
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Eur. J. Org. Chem. 2009, 6263−6276. (d) Debleds, O.; Gayon, E.;
Vrancken, E.; Campagne, J.-M. Beilstein J. Org. Chem. 2011, 7, 866−
877. (e) Nishibayashi, Y. Synthesis 2012, 44, 489−503.
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ASSOCIATED CONTENT
* Supporting Information
■
S
(7) (a) Detz, R. J.; Delville, M. M. E.; Hiemstra, H.; van Maarseveen,
J. H. Angew. Chem., Int. Ed. 2008, 47, 3777−3780. (b) Detz, R. J.;
Abiri, Z.; le Griel, R.; Hiemstra, H.; van Maarseveen, J. H. Chem.Eur.
J. 2011, 17, 5921−5930. (c) Hattori, G.; Matsuzawa, H.; Miyake, Y.;
Nishibayashi, Y. Angew. Chem., Int. Ed. 2008, 47, 3781−3783.
(d) Shibata, M.; Nakajima, K.; Nishibayashi, Y. Chem. Commun.
2014, 50, 7874−7877. (e) Hattori, G.; Sakata, K.; Matsuzawa, H.;
Tanabe, Y.; Miyake, Y.; Nishibayashi, Y. J. Am. Chem. Soc. 2010, 132,
10592.
General experimental conditions, NMR spectra, and HPLC
analysis of the products. This material is available free of charge
AUTHOR INFORMATION
Corresponding Authors
■
Notes
(8) (a) Fang, P.; Hou, X. L. Org. Lett. 2009, 11, 4612−4615.
(b) Zhang, C.; Hu, X. H.; Wang, Y. H.; Zheng, Z.; Xu, J.; Hu, X. P. J.
Am. Chem. Soc. 2012, 134, 9585−9588. (c) Zhu, F. L.; Zou, Y.; Zhang,
D. Y.; Wang, Y. H.; Hu, X. H.; Chen, S.; Xu, J.; Hu, X. P. Angew.
Chem., Int. Ed. 2014, 53, 1410−1414. (d) Han, F. Z.; Zhu, F. L.; Wang,
Y. H.; Zou, Y.; Hu, X. H.; Chen, S.; Hu, X. P. Org. Lett. 2014, 16, 588−
591. (e) Zhu, F. L.; Wang, Y. H.; Zhang, D. Y.; Hu, X. H.; Chen, S.;
Hou, C. J.; Xu, J.; Hu, X. P. Adv. Synth. Catal. DOI: 10.1002/
adsc.201400218. (f) Zhu, F. L.; Wang, Y. H.; Zhang, D. Y.; Xu, J.; Hu,
X. P. Angew. Chem., Int. Ed. 2014, 53, 10223−10227.
(9) In these cases, the propargylated products were of the same
polarity as the starting materials on TLC; therefore they were
subjected to cyclization with 1-azido-4-bromobenzene to facilitate
purification and characterization.
(10) CCDC-1014538 (for 3a) and CCDC-1022280 (for 3ag)
contain the supplementary crystallographic data for this paper. These
data can be obtained free of charge from The Cambridge
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We acknowledge research support from the National Natural
Science Foundation of China (No. 21272150 and No.
21072125). Dr. Hanwei Hu at Genchemistry is also gratefully
acknowledged for helpful discussions.
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dx.doi.org/10.1021/ol502615y | Org. Lett. XXXX, XXX, XXX−XXX