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Notes
trimethoxybenzene at −60 °C, although this reaction was found
The authors declare no competing financial interest.
to be much slower than that with thioanisole and required 2 h for
2
completion. The absorption and H NMR spectra of the final
ACKNOWLEDGMENTS
This study was supported by JSPS (Grant-in-Aid for Scientific
Research, Grant 22350030).
reaction solution showed the formation of a mixture of
(TPFP)FeIIICl and (TPFP)FeIIIOH (Figure S19), and product
analysis showed the formation of 1-chloro-2,4,6-trimethoxyben-
zene in 86% yield. Although the same compound was produced
in 47% yield with only TBAOCl at −60 °C, the result indicates
that 1 can chlorinate aromatic compounds. 1 was also mixed with
cyclohexene, but the reaction did not proceed at −60 °C. When
the reaction mixture was warmed to −20 °C, the reaction
proceeded to completion, affording a mixture of (TPFP)FeIIICl
and (TPFP)FeIIIOH (Figure S20). Product analysis showed the
formation of cyclohexene oxide, 2-cyclohexen-1-ol, and 2-
cyclohexen-1-one in yields of 63, 10, and 7%, respectively. 3-
Chlorocyclohexene was not produced in the reaction. At 0 °C,
the yield of cyclohexene oxide increased to 88%, but the yields of
other products were unchanged. The reaction with only
TBAOCl under the same conditions did not form cyclohexene
oxide but instead gave 2-cyclohexen-1-ol and 2-cyclohexen-1-one
in similar yields. The reaction with 18O-labeled 1 resulted in 18O
incorporation only in cyclohexene oxide (Figure S21). In
addition, while 1 reacted with cyclohexene within 3 min at
−20 °C, (TPFP)FeIVO formed from the decomposition of 1
required more than 90 min under the same conditions (Figure
S22). These results indicate that 1 oxidizes cyclohexene to
cyclohexene oxide and that the other products are due to side
reactions such as radical chain reactions with contaminated
oxygen gas. In fact, yields of >100% for 2-cyclohexen-1-ol and 2-
cyclohexen-1-one were obtained when the reaction was carried
out under air. Thus, 1 oxidizes olefins to epoxides.
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ASSOCIATED CONTENT
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S
* Supporting Information
Figure S1−S27 and experimental details. This material is
(17) Palmer, G. P. In Iron Porphyrins, Part II; Lever, A. B. P., Gray, H.
B., Eds.; Addison-Wesley: London, 1983.
AUTHOR INFORMATION
Corresponding Author
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dx.doi.org/10.1021/ja3108774 | J. Am. Chem. Soc. 2012, 134, 20617−20620