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diate E, which then abstracted a chlorine atom from a second
equivalent of 1b, giving dichlorides 3. Or, in the case of α-alkyl
groups, intermediate E was also subject to a competing hydro-
gen abstraction pathway, resulting in mixtures of 3 and chloro-
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Conclusion
In conclusion, we report here an efficient new process for the
chlorination of substituted phenylallene derivatives using the
hypervalent iodine reagent 1-chloro-1,2-benziodoxol-3-one
(1b). The reactions disclosed here represent the first report of a
regioselective chlorination of phenylallenes, in which the 2,3-
allene olefin undergoes selective vicinal dichlorination. Overall,
the reactions were mild and operationally-simple, tolerant to a
variety of different functional groups, and provided the prod-
ucts in typically good yield. The selectivity of the reaction is
presumably derived from it being a radical, not ionic, process,
which also enabled the formation of chlorodiene products with
α-alkyl substituted allenes. This reaction offers a new strategy
for accessing dichlorinated functional group building blocks not
readily accessible with other reagents, and our continued work
in this area will be disclosed in due course.
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Acknowledgements
This work was supported by the Natural Sciences and Engi-
neering Research Council (NSERC) of Canada and the Univer-
sity of Waterloo. We also thank Val Goodfellow of the
UWaterloo Mass Spectrometry Facility.
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