Organic Letters
Letter
Scheme 3. Total Synthesis of Cardiopetaline via Wagner−
Meerwein Rearrangement of the Sulfonyloxirane
ACKNOWLEDGMENTS
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This work was financially supported by JSPS KAKENHI (Grant
Nos. 25221301, 26713001), Platform for Drug Discovery,
Informatics, and Structural Life Science from the Ministry of
Education, Culture, Sports, Science and Technology, Japan.
Y.N. was supported by research fellowships from JSPS.
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completing the first total synthesis of (−)-cardiopetaline (7).
The synthetic cardiopetaline was identical in all respects to the
corresponding natural product.
In summary, we have achieved a concise synthesis of
(−)-cardiopetaline by means of a Wagner−Meerwein rear-
rangement of a sulfonyloxirane. The synthetic strategy, via
rearrangement of the sulfonyloxirane, offers the following
advantages: (1) the oxygen functionalities could be easily
introduced through the stereoselective nucleophilic epoxida-
tion, (2) the sulfonyl group stabilized the oxirane ring under
acidic conditions and may facilitate the regioselective cleavage
of the oxirane ring,24 and (3) the rearrangement could be
carried out in methanol, which efficiently captured the cationic
intermediate, leading to the introduction of the oxygen atom of
the tertiary alcohol in the natural product.
ASSOCIATED CONTENT
* Supporting Information
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S
The Supporting Information is available free of charge on the
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AUTHOR INFORMATION
Corresponding Authors
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Am. Chem. Soc. 2013, 135, 14313.
Present Address
§(Y.N.) Institute of Biomaterials and Bioengineering, Tokyo
Medical and Dental University, 2-3-10 Kanda-Surugadai,
Chiyoda-ku, Tokyo, 101-0062, Japan
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Notes
The authors declare no competing financial interest.
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