Organic Letters
Letter
different double bonds can also be reduced successively if
needed.
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The CC double bond could also be oxidized by m-CPBA
to give the corresponding epoxidation product 4 in 70% yield
without any loss in enantioselectivity.15 Furthermore, the
transformation could be performed at the hydroxyl group, and
2a could be transformed to 5, with opposite configuration, via
a Mitsunobu reaction.8 The hydroxyl group of 2a could also be
acetylated by Ac2O easily to give 6, which was then treated
with CH3MgBr, providing the alkylated product 7 in high yield
and 95% ee (Scheme 4).16
In summary, we have developed an efficient RuPHOX−Ru-
catalyzed selective asymmetric hydrogenation of four-mem-
bered exo-α,β-unsaturated cyclobutanones. The reduced
products were obtained in almost quantitative yields and up
to 99.9% ee under mild reaction conditions. The reaction
could be performed on a gram scale with a relatively low
catalyst loading (up to 10000 S/C), and the resulting product
can be transformed to several biologically active compounds.
Combined with our previous work, we can selectively
hydrogenate the CO or CC double bonds of four-
membered exo-α,β-unsaturated cyclobutanones. The two
different double bonds can also be reduced successively if
required.
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ASSOCIATED CONTENT
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S
* Supporting Information
The Supporting Information is available free of charge on the
Experimental procedures and spectral data for all new
Accession Codes
CCDC 1899684 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
AUTHOR INFORMATION
■
Corresponding Authors
ORCID
Notes
(6) (a) Xie, J.-B.; Xie, J.-H.; Liu, X.-Y.; Kong, W.-L.; Li, S.; Zhou, Q.-
L. J. Am. Chem. Soc. 2010, 132, 4538. (b) Wang, Y.; Yang, G.; Xie, F.;
Zhang, W. Org. Lett. 2018, 20, 6135.
The authors declare no competing financial interest.
(7) (a) Toelle, N.; Weinstabl, H.; Gaich, T.; Mulzer, J. Angew.
Chem., Int. Ed. 2014, 53, 3859. (b) Pettit, G. R.; Meng, Y.; Pettit, R.
K.; Herald, D. L.; Hogan, F.; Cichacz, Z. A. Bioorg. Med. Chem. 2010,
18, 4879.
(8) Danappe, S.; Pal, A.; Alexandre, C.; Aubertin, A.-M.;
Bourgougnon, N.; Huet, F. Tetrahedron 2005, 61, 5782.
ACKNOWLEDGMENTS
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This work was partially supported by the National Natural
Science Foundation of China (Nos. 21672142, 21620102003,
and 21831005) and the Shanghai Municipal Education
Commission (No. 201701070002E00030). We also thank
the Instrumental Analysis Center of Shanghai Jiao Tong
University.
(9) Xia, J.; Nie, Y.; Liu, Y.; Gridnev, I. D.; Zhang, W. Chin. J. Chem.
2018, 36, 612.
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