Divergent Reactivity during the Trapping of Benzynes by Glycidol Analogs

Ring Cleavage via Pinacol-Like Rearrangements vs Oxirane Fragmentations

Juntian Zhang, Thomas R Hoye

Research output: Contribution to journalArticle

Abstract

Hydroxy-containing cyclic ethers react with thermally generated benzynes to produce aryl ethers. Diverse reactivity was observed. Cleavage of the cyclic ether was involved in most of the pathways. The transformations are rationalized via initial formation of oxonium ion-containing 1,3-zwitterions arising from preferential nucleophilic attack on the benzyne by the ether oxygen. Pinacol-like rearrangements, including ring expansion, to yield aldehydes or ketones and oxirane fragmentations to generate aryl enol ethers were main competing events.

Original languageEnglish (US)
Pages (from-to)2615-2619
Number of pages5
JournalOrganic Letters
Volume21
Issue number8
DOIs
StatePublished - Apr 19 2019

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glycidol
Cyclic Ethers
Ethylene Oxide
Ethers
cleavage
ethers
fragmentation
reactivity
trapping
analogs
rings
Ketones
Aldehydes
Ether
Ions
Oxygen
zwitterions
aldehydes
ketones
attack

Cite this

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title = "Divergent Reactivity during the Trapping of Benzynes by Glycidol Analogs: Ring Cleavage via Pinacol-Like Rearrangements vs Oxirane Fragmentations",
abstract = "Hydroxy-containing cyclic ethers react with thermally generated benzynes to produce aryl ethers. Diverse reactivity was observed. Cleavage of the cyclic ether was involved in most of the pathways. The transformations are rationalized via initial formation of oxonium ion-containing 1,3-zwitterions arising from preferential nucleophilic attack on the benzyne by the ether oxygen. Pinacol-like rearrangements, including ring expansion, to yield aldehydes or ketones and oxirane fragmentations to generate aryl enol ethers were main competing events.",
author = "Juntian Zhang and Hoye, {Thomas R}",
year = "2019",
month = "4",
day = "19",
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volume = "21",
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journal = "Organic Letters",
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T1 - Divergent Reactivity during the Trapping of Benzynes by Glycidol Analogs

T2 - Ring Cleavage via Pinacol-Like Rearrangements vs Oxirane Fragmentations

AU - Zhang, Juntian

AU - Hoye, Thomas R

PY - 2019/4/19

Y1 - 2019/4/19

N2 - Hydroxy-containing cyclic ethers react with thermally generated benzynes to produce aryl ethers. Diverse reactivity was observed. Cleavage of the cyclic ether was involved in most of the pathways. The transformations are rationalized via initial formation of oxonium ion-containing 1,3-zwitterions arising from preferential nucleophilic attack on the benzyne by the ether oxygen. Pinacol-like rearrangements, including ring expansion, to yield aldehydes or ketones and oxirane fragmentations to generate aryl enol ethers were main competing events.

AB - Hydroxy-containing cyclic ethers react with thermally generated benzynes to produce aryl ethers. Diverse reactivity was observed. Cleavage of the cyclic ether was involved in most of the pathways. The transformations are rationalized via initial formation of oxonium ion-containing 1,3-zwitterions arising from preferential nucleophilic attack on the benzyne by the ether oxygen. Pinacol-like rearrangements, including ring expansion, to yield aldehydes or ketones and oxirane fragmentations to generate aryl enol ethers were main competing events.

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