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

5 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).

PubMed: MeSH publication types

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

Access

10.1021/acs.orglett.9b00215

Fingerprint Dive into the research topics of 'Benzyne Cascade Reactions via Benzoxetenonium Ions and Their Rearrangements to o-Quinone Methides'. Together they form a unique fingerprint.

Cite this

@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.}",

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).",

year = "2019",

month = mar,

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.

N1 - 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).

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

C2 - 30829492

AN - SCOPUS:85062832678

VL - 21

SP - 1672

EP - 1675

JO - Organic Letters

JF - Organic Letters

SN - 1523-7060

IS - 6

ER -