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Published on: February 16, 2018
Benzyne Cascade Reactions via Benzoxetenonium Ions and Their Rearrangements to o-Quinone Methides
Hang Shen1, Xiao Xiao1, Thomas R Hoye1
1Department of Chemistry , University of Minnesota , 207 Pleasant Street SE , Minneapolis , Minnesota 55455 , United States.
Abstract:
A new thermal isomerization of polyynes is described. Benzyne intermediates substituted by a C(RR')OR'' substituent adjacent to one of the benzyne sp-hybridized carbons give rise to products in which the OR' moiety has migrated to the proximal benzyne carbon. This process likely proceeds via sequential formation of multiple reactive intermediates: an initial thermally generated benzyne, a strained benzoxetenonium ion, and an o-quinone methide. As some examples demonstrate, the overall transformation can be quite efficient. The mechanism of this novel reaction is further supported by experiments and DFT calculations.
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