Organic Letters
Letter
This result displays a difference to the protonation reaction that
proceeded in the absence of an additive at lower temperatures
to give rather the kinetic adduct 20. Similar results were
observed with pyrrolidine as the nucleophile to afford 21 and
22 as a thermodynamic and a kinetic product, respectively
(entries 3, 4).
ACKNOWLEDGMENTS
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We thank Prof. Masahiko Hayashi (Kobe Univ.) for helpful
discussions. Financial support for this research was provided by
Grants-in-Aid (23590003 and 20002004) and Platform for
Drug Discovery, Informatics, and Structural Life Science from
the Ministry of Education, Culture, Sports, Science and
Technology of Japan.
The diastereoselective transformation of (−)-myrtenal (23)
was next examined (Scheme 6). Heating at 70 °C yielded
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Scheme 6. Redox Transformation of (−)-Myrtenal
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a
An inseparable mixture of 25 and 26 was obtained.
primarily the thermodynamically more stable trans product 25
(entry 1). This preference was reversed to give 26 when the
reaction was performed at 0 °C (entry 2). The use of
pyrrolidine as a nucleophile resulted in the protonation of 24
on both sides to give a diastereomeric mixture of 27 and 28 at
70 °C (entry 3). This result most likely stemmed from the fact
that the kinetic intermediate, the cis acyl cyanide, did not fully
isomerize prior to the formation of amide. On the other hand,
the kinetic product 28 was obtained at −20 °C with very high
selectivity and in very good yield (entry 4). This result
underscores the potential utility of the present method for
constructing complicated cyclic molecular structures.
In conclusion, we have established a useful method for the
redox transformation of an α,β-unsaturated aldehyde to a
carboxylic acid derivative using a combination of TMSCN and
DBU. A variety of carboxylic acid derivatives could be
synthesized from α,β-unsaturated aldehydes. Application of
the present method to the total synthesis of complex molecules
is currently underway in our laboratories.
ASSOCIATED CONTENT
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S
* Supporting Information
Experimental details and spectroscopic data (PDF). This
material is available free of charge via the Internet at http://
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(b) Hayashi, M.; Kawabata, H.; Yoshimoto, K.; Tanaka, T. Phosphorus,
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AUTHOR INFORMATION
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Corresponding Author
(6) Kobayashi, S.; Tsuchiya, Y.; Mukaiyama, T. Chem. Lett. 1991,
537.
Notes
(7) Hunig, S.; Schaller, R. Angew. Chem., Int. Ed. Engl. 1982, 21, 36.
̈
(8) Hunig, S.; Reichelt, H. Chem. Ber. 1986, 119, 1772.
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The authors declare no competing financial interest.
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dx.doi.org/10.1021/ol403415z | Org. Lett. XXXX, XXX, XXX−XXX