Alkynyliodonium salts in organic synthesis, dihydrofuran formation via a formal stevens shift of a carbon substituent within a disubstituted-carbon oxonium ylide

Ken S. Feldman, M. L. Wrobleski

Research output: Contribution to journalArticle

41 Citations (Scopus)

Abstract

The addition of p-toluenesulfinate to the silyl, 1-furanyl, and 1-pyranyl ethers of 1-hydroxybut-3-ynyl(phenyl)iodonium triflate triggers a sequence of reactions that ultimately delivers 2-substituted 3-p-toluenesulfonyldihydrofuran products in variable yields. A putative 1,2-group shift within an unsaturated oxonium ylide (Stevens rearrangement) accounts for the oxygen-to-carbon transfer of the ether substituent. Deuterium labeling studies clarify the mechanistic course of this shift by providing evidence consistent with intramolecular substituent transfer and by identifying the primary source of the proton that intercepts the ylide in the major yield-limiting process.

Original languageEnglish (US)
Pages (from-to)8659-8668
Number of pages10
JournalJournal of Organic Chemistry
Volume65
Issue number25
DOIs
StatePublished - Dec 15 2000

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Ethers
Deuterium
Ether
Labeling
Protons
Carbon
Salts
Oxygen
hydronium ion

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

Cite this

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title = "Alkynyliodonium salts in organic synthesis, dihydrofuran formation via a formal stevens shift of a carbon substituent within a disubstituted-carbon oxonium ylide",
abstract = "The addition of p-toluenesulfinate to the silyl, 1-furanyl, and 1-pyranyl ethers of 1-hydroxybut-3-ynyl(phenyl)iodonium triflate triggers a sequence of reactions that ultimately delivers 2-substituted 3-p-toluenesulfonyldihydrofuran products in variable yields. A putative 1,2-group shift within an unsaturated oxonium ylide (Stevens rearrangement) accounts for the oxygen-to-carbon transfer of the ether substituent. Deuterium labeling studies clarify the mechanistic course of this shift by providing evidence consistent with intramolecular substituent transfer and by identifying the primary source of the proton that intercepts the ylide in the major yield-limiting process.",
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Alkynyliodonium salts in organic synthesis, dihydrofuran formation via a formal stevens shift of a carbon substituent within a disubstituted-carbon oxonium ylide. / Feldman, Ken S.; Wrobleski, M. L.

In: Journal of Organic Chemistry, Vol. 65, No. 25, 15.12.2000, p. 8659-8668.

Research output: Contribution to journalArticle

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T1 - Alkynyliodonium salts in organic synthesis, dihydrofuran formation via a formal stevens shift of a carbon substituent within a disubstituted-carbon oxonium ylide

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AB - The addition of p-toluenesulfinate to the silyl, 1-furanyl, and 1-pyranyl ethers of 1-hydroxybut-3-ynyl(phenyl)iodonium triflate triggers a sequence of reactions that ultimately delivers 2-substituted 3-p-toluenesulfonyldihydrofuran products in variable yields. A putative 1,2-group shift within an unsaturated oxonium ylide (Stevens rearrangement) accounts for the oxygen-to-carbon transfer of the ether substituent. Deuterium labeling studies clarify the mechanistic course of this shift by providing evidence consistent with intramolecular substituent transfer and by identifying the primary source of the proton that intercepts the ylide in the major yield-limiting process.

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