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 | |
| State | Published - Mar 15 2019 |
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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 journal › Article
}
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.
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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 -