C O M M U N I C A T I O N S
Table 1. Generation of a Pool of 2a
Table 2. Generation of Dications and Their Reaction with
Nucleophilesa
a Reactions were usually carried out with 0.4 mmol of a precursor. After
the electrolysis (2.5 F/mol) at -78 °C, a nucleophile (5.0 equiv) was added
at the same temperature. b Isolated yields. c The electrolysis and the follow-
up reaction were carried out at -48 °C. d A mixture of isomers. e The
electrolysis was carried out at -15 °C, and the follow-up reaction was
carried out at -78 °C.
a Reactions were usually carried out with 0.4 mmol of substrate and 2.5
equiv of allyltrimethylsilane. b Yields were determined by GC.
Yoshida, J. Org. Lett. 2004, 6, 3755-3758. (l) Suga, S.; Suzuki, S.;
Maruyama, T.; Yoshida, J. Bull. Chem. Soc. Jpn. 2004, 77, 1545-1554.
(m) Suga, S.; Nishida, T.; Yamada, D.; Nagaki, A.; Yoshida, J. J. Am.
Chem. Soc. 2004, 126, 14338-14339. (n) Nagaki, A.; Kawamura, K.;
Suga, S.; Ando, T.; Sawamoto, M.; Yoshida, J. J. Am. Chem. Soc. 2004,
126, 14702-14703.
Figure 1. 13C NMR spectrum of 11 (in CD2Cl2, -80 °C).
(2) Reviews: (a) Schmittel, M.; Burghart, A. Angew. Chem., Int. Ed. Engl.
1997, 36, 2550-2589. (b) Baciocchi, E.; Bietti, M.; Lanzalunga, O. Acc.
Chem. Res. 2000, 33, 243-251.
anodic oxidation of 17 (Eox ) 1.45 V) followed by the reaction
with allyltrimethylsilane also proceeded smoothly to give the desired
diallylated product 18 in good yield. In summary, the present
observations illustrate the potential of a new approach for the
generation of cation pools, which involves C-C bond dissociation
in the radial cation intermediates. It is also noteworthy that the
method opens a simple and straightforward approach to dications
under mild conditions. Further work is in progress to explore the
full range of applicability of the present approach.
(3) Mechanistic studies: (a) Camaioni, D. M.; Franz, J. A. J. Org. Chem.
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(h) Freccero, M.; Pratt, A.; Albini, A.; Long, C. J. Am. Chem. Soc. 1998,
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(e) Nenajdenko, V. G.; Shevchenko, N. E.; Balenkova, E. S. Chem. ReV.
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Acknowledgment. This work was partially supported by the
Grant-in-Aid for Scientific Research.
Supporting Information Available: Experimental procedures and
analytical and spectroscopic data (PDF). This material is available free
References
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