Organic Letters
Letter
(12) For reviews, see: (a) Avalos, M.; Babiano, R.; Cintas, P.; Jimen
́
ez,
yield with 99/1 dr and 92% ee. The next translactonization
proceeded smoothly to give β,γ-disubstituted lactone 4 with
preservation of dr and ee.28 The Jones’ oxidation delivered the
(+)-methylenolactocin 5 in 82% yield.
In conclusion, a highly enantioselective synthesis of α-exo-
methylene γ-butyrolactones has been achieved through asym-
metric chromium-catalyzed 2-(alkoxycarbonyl)allylation of
aldehydes and lactonization. The synthetic utilities are
demonstrated by two short transformations and enantioselective
syntheses of (+)-methylenolactocin. Future work will focus on
expanding this catalytic system to other chromium-mediated
transformations and applying this protocol to the synthesis of
complex molecules with biological and medicinal significance.
J. L.; Palacios, J. C. Chem. Soc. Rev. 1999, 28, 169. (b) Furstner, A. Chem.
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Rev. 1999, 99, 991 and references cited therein.
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Ed. 2003, 42, 1032. Oxazoline/sulfonamide system: (f) Chen, C.;
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763. (n) McManus, H. A.; Guiry, P. J. J. Org. Chem. 2002, 67, 8566−
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ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
■
S
AUTHOR INFORMATION
Corresponding Author
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We are grateful to NSFC-21421091, the “Thousand Plan” Youth
program, State Key Laboratory of Organometallic Chemistry,
Shanghai Institute of Organic Chemistry, Chinese Academy of
Sciences. We thank Professor Yoshito Kishi (Harvard Uni-
versity) for valuable comments.
(15) Deng, Q.-H.; Melen, R. L.; Gade, L. H. Acc. Chem. Res. 2014, 47,
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