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

Hang Shen, Xiao Xiao, Thomas R Hoye

Research output: Contribution to journalArticle

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 languageEnglish (US)
Pages (from-to)1672-1675
Number of pages4
JournalOrganic Letters
Volume21
Issue number6
DOIs
StatePublished - Mar 15 2019

Fingerprint

quinones
cascades
Ions
carbon
isomerization
ions
Carbon
Polyacetylenes
products
Isomerization
Discrete Fourier transforms
Hot Temperature
quinone methide
benzyne
Experiments

PubMed: MeSH publication types

  • Journal Article
  • Research Support, N.I.H., Extramural
  • Research Support, U.S. Gov't, Non-P.H.S.

Cite this

Benzyne Cascade Reactions via Benzoxetenonium Ions and Their Rearrangements to o-Quinone Methides. / Shen, Hang; Xiao, Xiao; Hoye, Thomas R.

In: Organic Letters, Vol. 21, No. 6, 15.03.2019, p. 1672-1675.

Research output: Contribution to journalArticle

@article{90ed969dc4c44f2da789158b05f7327d,
title = "Benzyne Cascade Reactions via Benzoxetenonium Ions and Their Rearrangements to o-Quinone Methides",
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.",
author = "Hang Shen and Xiao Xiao and Hoye, {Thomas R}",
year = "2019",
month = "3",
day = "15",
doi = "10.1021/acs.orglett.9b00215",
language = "English (US)",
volume = "21",
pages = "1672--1675",
journal = "Organic Letters",
issn = "1523-7060",
publisher = "American Chemical Society",
number = "6",

}

TY - JOUR

T1 - Benzyne Cascade Reactions via Benzoxetenonium Ions and Their Rearrangements to o-Quinone Methides

AU - Shen, Hang

AU - Xiao, Xiao

AU - Hoye, Thomas R

PY - 2019/3/15

Y1 - 2019/3/15

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=85062832678&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85062832678&partnerID=8YFLogxK

U2 - 10.1021/acs.orglett.9b00215

DO - 10.1021/acs.orglett.9b00215

M3 - Article

VL - 21

SP - 1672

EP - 1675

JO - Organic Letters

JF - Organic Letters

SN - 1523-7060

IS - 6

ER -