Organic Letters
Letter
Pazdzierniok-Holewa, A.; Zielin
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ska, K.; Simka, W.; Gajos, A.;
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Scheme 5. Synthesis of Saccharin and Phthalimide
Derivatives
Szymura, K. J. Org. Chem. 2012, 77, 1952 and references therein.
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Gonzal
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̃
In conclusion, we report the development of decarboxylative
oxygenation and nitrogenation of β,γ-unsaturated carboxylic
acids mediated by hypervalent iodine reagents. Based on
mechanistic investigations, hypervalent iodine reagents appear
to be unique for use in ionic oxidative decarboxylation. Further
investigation focused on expanding the scope of substrates of
this method is currently in progress.
7242. (d) Lishchynskyi, A.; Muniz, K. Chem.Eur. J. 2012, 18, 2213.
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(e) Souto, J. A.; Gonzal
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ez, Y.; Iglesias, A.; Zian, D.; Lishchynskyi, A.;
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A.; Martínez, C.; Velilla, I.; Muniz, K. Angew. Chem., Int. Ed. 2013, 52,
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ASSOCIATED CONTENT
* Supporting Information
Detailed experimental procedures and spectral data for all new
compounds are provided. This material is available free of
(12) Detailed results of solvent screening are shown in the
Supporting Information.
■
S
(13) Singh, F. V.; Rehbein, J.; Wirth, T. ChemistryOpen 2012, 1, 245.
(14) (a) Zefirov, N. S.; Safronov, S. O.; Kaznacheev, A. A.; Zhdankin,
V. V. Zh. Org. Khim. 1989, 25, 1807. (b) Lutz, K. E.; Thomson, R. J.
Angew. Chem., Int. Ed. 2011, 50, 4437. (c) Farid, U.; Wirth, T. Angew.
Chem., Int. Ed. 2012, 51, 3462.
AUTHOR INFORMATION
Corresponding Author
(15) Most of the reactions gave 2 as products, with a small amount of
homocoupling product 3. Detailed results were described in the
Supporting Information.
(16) The reaction using β,γ-disubstituted β,γ-unsaturated carboxylic
acid, 2-(3,4-dihydronaphthalen-1-yl)acetic acid, gave the product as a
mixture of regioisomers in low yield. See the Supporting Information
for details.
■
Notes
The authors declare no competing financial interest.
(17) When the reaction using 1v was carried out for a shorter
reaction time (3 h), a 51% yield was obtained with a γ/α ratio of
69:31. The change in the γ/α ratio indicates that the isomerization of
α-2v to the thermodynamically more stable γ-2v occurred under the
reaction conditions. The acid-catalyzed isomerization of allylic acetates
has been reported; see: (a) Young, W. G.; Webb, I. D. J. Am. Chem.
Soc. 1951, 73, 780. (b) Young, W. G.; Green, H. E.; Diaz, A. F. J. Am.
Chem. Soc. 1971, 93, 4782.
ACKNOWLEDGMENTS
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This work was supported by Grants-in-Aid for Scientific
Research (Nos. 25288047 and 26105735) from the the
Ministry of Education, Culture, Sports, Science, and Technol-
ogy (MEXT), Japan and by a research Grant from the Society
of Iodine Science.
(18) See the Supporting Information for details.
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dx.doi.org/10.1021/ol5022433 | Org. Lett. XXXX, XXX, XXX−XXX