Benzyne Cascade Reactions via Benzoxetenonium Ions and Their Rearrangements to o-Quinone Methides

Hang Shen; Xiao Xiao; Thomas R. Hoye

doi:10.1021/acs.orglett.9b00215

Benzyne Cascade Reactions via Benzoxetenonium Ions and Their Rearrangements to o-Quinone Methides

Hang Shen, Xiao Xiao, Thomas R. Hoye

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

10 Scopus citations

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.

Original language	English (US)
Pages (from-to)	1672-1675
Number of pages	4
Journal	Organic Letters
Volume	21
Issue number	6
DOIs	https://doi.org/10.1021/acs.orglett.9b00215
State	Published - Mar 15 2019

Bibliographical note

Funding Information:
This work was supported by the Institute of General Medical Sciences of the U.S. Department of Health and Human Services (R35 GM127097) and the National Science Foundation (CHE-1665389). Most of the NMR data were obtained with an instrument acquired through the NIH Shared Instrumentation Grant program (S10OD011952).

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© 2019 American Chemical Society.

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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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Benzyne Cascade Reactions via Benzoxetenonium Ions and Their Rearrangements to o-Quinone Methides

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