Intramolecular Alkene Fluoroarylation of Phenolic Ethers Enabled by Electrochemically Generated Iodane

Alastair J J Lennox; Sayad Doobary; Darren L. Poole

doi:10.1021/acs.joc.1c01946

Intramolecular Alkene Fluoroarylation of Phenolic Ethers Enabled by Electrochemically Generated Iodane

Alastair J J Lennox^*, Sayad Doobary, Darren L. Poole

^*Corresponding author for this work

Research output: Contribution to journal › Article (Academic Journal) › peer-review

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Abstract

The 3-substituted chromane core is found in several bioactive natural products. Herein, we describe a route to 3-fluorinated chromanes from allylic phenol ethers. Our external oxidant-free approach takes advantage of an electro-chemical generation of a hypervalent iodine species, difluoro-λ3-tolyl iodane, which mediates the alkene fluoroaryla-tion. High yields and selectivity for this transformation are achieved for electron poor substrates. The redox chemistry has been characterized for the electrochemical generation of the iodane in the presence of fluoride, and insights into the mechanism are given. The transformation has been demonstrated on larger gram scales, which represents the potential broader utility of the process.

Original language	English
Pages (from-to)	16095-16103
Number of pages	9
Journal	Journal of Organic Chemistry
Volume	86
Issue number	22
Early online date	12 Nov 2021
DOIs	https://doi.org/10.1021/acs.joc.1c01946
Publication status	Published - 19 Nov 2021

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Fluorofunctionalisation of alkenes via electrochemically generated hypervalent iodine reagents
Doobary, S. (Author), Lennox, A. (Supervisor) & Fermin, D. J. (Supervisor), 25 Jan 2022
Student thesis: Doctoral Thesis › Doctor of Philosophy (PhD)

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abstract = "The 3-substituted chromane core is found in several bioactive natural products. Herein, we describe a route to 3-fluorinated chromanes from allylic phenol ethers. Our external oxidant-free approach takes advantage of an electro-chemical generation of a hypervalent iodine species, difluoro-λ3-tolyl iodane, which mediates the alkene fluoroaryla-tion. High yields and selectivity for this transformation are achieved for electron poor substrates. The redox chemistry has been characterized for the electrochemical generation of the iodane in the presence of fluoride, and insights into the mechanism are given. The transformation has been demonstrated on larger gram scales, which represents the potential broader utility of the process.",

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AU - Lennox, Alastair J J

AU - Doobary, Sayad

AU - Poole, Darren L.

PY - 2021/11/19

Y1 - 2021/11/19

N2 - The 3-substituted chromane core is found in several bioactive natural products. Herein, we describe a route to 3-fluorinated chromanes from allylic phenol ethers. Our external oxidant-free approach takes advantage of an electro-chemical generation of a hypervalent iodine species, difluoro-λ3-tolyl iodane, which mediates the alkene fluoroaryla-tion. High yields and selectivity for this transformation are achieved for electron poor substrates. The redox chemistry has been characterized for the electrochemical generation of the iodane in the presence of fluoride, and insights into the mechanism are given. The transformation has been demonstrated on larger gram scales, which represents the potential broader utility of the process.

AB - The 3-substituted chromane core is found in several bioactive natural products. Herein, we describe a route to 3-fluorinated chromanes from allylic phenol ethers. Our external oxidant-free approach takes advantage of an electro-chemical generation of a hypervalent iodine species, difluoro-λ3-tolyl iodane, which mediates the alkene fluoroaryla-tion. High yields and selectivity for this transformation are achieved for electron poor substrates. The redox chemistry has been characterized for the electrochemical generation of the iodane in the presence of fluoride, and insights into the mechanism are given. The transformation has been demonstrated on larger gram scales, which represents the potential broader utility of the process.

U2 - 10.1021/acs.joc.1c01946

DO - 10.1021/acs.joc.1c01946

M3 - Article (Academic Journal)

C2 - 34766770

SN - 0022-3263

VL - 86

SP - 16095

EP - 16103

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

IS - 22

ER -

Intramolecular Alkene Fluoroarylation of Phenolic Ethers Enabled by Electrochemically Generated Iodane

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Fluorofunctionalisation of alkenes via electrochemically generated hypervalent iodine reagents

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