Journal of the American Chemical Society
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minor pathway after [2+2] cycloaddition.6g Therefore, we
postulated that allyl group migration on intermediate i oc-
curs readily so as to promote a consequent oxonium Claisen
rearrangement prior to ring opening step. Surprisingly, there
is no observation of any thio-Claisen rearrangement product
in this transformation, supporting the hypothesis that inter-
mediates ii and vii might not be generated in the reaction.
Moreover, as shown by the structures of 3p, 3r, and 3s, the
overall process has a net allylic shift as a standard ortho-
Claisen rearrangement. Because the concerted nature of or-
tho-Claisen rearrangement requires the same allyl group
conversion, the allyl SꢀO migration step in this transfor-
mation has to be a direct 1,2-shift. Although uncommon, an
ion-pair migration mechanism was previously observed in
the Mislow-Evans rearrangement with cinnamyl group.12
(3) For selected examples, see: a) Hoye, T. R.; Baire, B.; Niu,
1
2
3
4
5
6
7
8
D.; Willoughby, P. H.; Woods, B. P. Nature 2012, 490, 208-212; b)
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9
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26
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28
29
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In summary, a tandem aryne S=O bond insertion/C-H
functionalization process was successfully developed, featur-
ing arene 1,2,3-trisubstitution from relatively simple aryl allyl
sulfoxide. This transformation proceeded through an un-
precedented formation of C-S, C-O, and C-C bonds on three
consecutive positions of an arene ring. The reaction condi-
tion is mild and efficient with a broad substrate scope. Pre-
liminary mechanistic investigation suggests that the reaction
might occur through an allyl SꢀO migration on a four-
membered intermediate with a consequent Claisen rear-
rangement. Future work of our study involves the in-depth
mechanistic study of this transformation as well as the de-
velopment of other aryne cascade processes.
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ASSOCIATED CONTENT
Supporting Information. Experimental details for all chem-
ical reactions and measurements and X-ray single crystallo-
graphic data. This material is available free of charge via the
AUTHOR INFORMATION
Corresponding Author
Author Contributions
†Li, Y. and Qiu, D. contributed equally to this work.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
The authors gratefully acknowledge research support of this
work by NSFC (21372268) and Fundamental Research Funds
for the Central Universities (106112016CDJZR228806).
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