Nickel-Catalyzed Decarbonylative Synthesis of Fluoroalkyl Thioethers

Conor E. Brigham; Christian A. Malapit; Naish Lalloo; Melanie S. Sanford

doi:10.1021/acscatal.0c02950

Nickel-Catalyzed Decarbonylative Synthesis of Fluoroalkyl Thioethers

Conor E. Brigham, Christian A. Malapit, Naish Lalloo, Melanie S. Sanford

Chemistry

Research output: Contribution to journal › Article › peer-review

55 Scopus citations

Abstract

This report describes the development of a nickel-catalyzed decarbonylative reaction for the synthesis of fluoroalkyl thioethers (RFSR) from the corresponding thioesters. Readily available, inexpensive, and stable fluoroalkyl carboxylic acids (RFCO2H) serve as the fluoroalkyl (RF) source in this transformation. Stoichiometric organometallic studies reveal that RF-S bond-forming reductive elimination is a challenging step in the catalytic cycle. This led to the identification of diphenylphosphinoferrocene as the optimal ligand for this transformation. Ultimately, this method was applied to the construction of diverse fluoroalkyl thioethers (RFSR), with R = both aryl and alkyl.

Original language	English (US)
Pages (from-to)	8315-8320
Number of pages	6
Journal	ACS Catalysis
Volume	10
Issue number	15
DOIs	https://doi.org/10.1021/acscatal.0c02950
State	Published - Aug 7 2020

Funding

We acknowledge financial support from NIH NIGMS (GM073836 and GM136332) and the Danish National Research Foundation (Carbon Dioxide Activation Center; CADIAC) for support.

Keywords

decarbonylation
fluoroalkyl carboxylic acids
fluoroalkylation
nickel-catalysis
thioether synthesis

ASJC Scopus subject areas

General Chemistry
Catalysis

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10.1021/acscatal.0c02950

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title = "Nickel-Catalyzed Decarbonylative Synthesis of Fluoroalkyl Thioethers",

abstract = "This report describes the development of a nickel-catalyzed decarbonylative reaction for the synthesis of fluoroalkyl thioethers (RFSR) from the corresponding thioesters. Readily available, inexpensive, and stable fluoroalkyl carboxylic acids (RFCO2H) serve as the fluoroalkyl (RF) source in this transformation. Stoichiometric organometallic studies reveal that RF-S bond-forming reductive elimination is a challenging step in the catalytic cycle. This led to the identification of diphenylphosphinoferrocene as the optimal ligand for this transformation. Ultimately, this method was applied to the construction of diverse fluoroalkyl thioethers (RFSR), with R = both aryl and alkyl.",

keywords = "decarbonylation, fluoroalkyl carboxylic acids, fluoroalkylation, nickel-catalysis, thioether synthesis",

author = "Brigham, {Conor E.} and Malapit, {Christian A.} and Naish Lalloo and Sanford, {Melanie S.}",

note = "Funding Information: We acknowledge financial support from NIH NIGMS (GM073836 and GM136332) and the Danish National Research Foundation (Carbon Dioxide Activation Center; CADIAC) for support. Publisher Copyright: Copyright {\textcopyright} 2020 American Chemical Society.",

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AU - Brigham, Conor E.

AU - Malapit, Christian A.

AU - Lalloo, Naish

AU - Sanford, Melanie S.

N1 - Funding Information: We acknowledge financial support from NIH NIGMS (GM073836 and GM136332) and the Danish National Research Foundation (Carbon Dioxide Activation Center; CADIAC) for support. Publisher Copyright: Copyright © 2020 American Chemical Society.

PY - 2020/8/7

Y1 - 2020/8/7

N2 - This report describes the development of a nickel-catalyzed decarbonylative reaction for the synthesis of fluoroalkyl thioethers (RFSR) from the corresponding thioesters. Readily available, inexpensive, and stable fluoroalkyl carboxylic acids (RFCO2H) serve as the fluoroalkyl (RF) source in this transformation. Stoichiometric organometallic studies reveal that RF-S bond-forming reductive elimination is a challenging step in the catalytic cycle. This led to the identification of diphenylphosphinoferrocene as the optimal ligand for this transformation. Ultimately, this method was applied to the construction of diverse fluoroalkyl thioethers (RFSR), with R = both aryl and alkyl.

AB - This report describes the development of a nickel-catalyzed decarbonylative reaction for the synthesis of fluoroalkyl thioethers (RFSR) from the corresponding thioesters. Readily available, inexpensive, and stable fluoroalkyl carboxylic acids (RFCO2H) serve as the fluoroalkyl (RF) source in this transformation. Stoichiometric organometallic studies reveal that RF-S bond-forming reductive elimination is a challenging step in the catalytic cycle. This led to the identification of diphenylphosphinoferrocene as the optimal ligand for this transformation. Ultimately, this method was applied to the construction of diverse fluoroalkyl thioethers (RFSR), with R = both aryl and alkyl.

KW - decarbonylation

KW - fluoroalkyl carboxylic acids

KW - fluoroalkylation

KW - nickel-catalysis

KW - thioether synthesis

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JO - ACS Catalysis

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ER -

Nickel-Catalyzed Decarbonylative Synthesis of Fluoroalkyl Thioethers

Abstract

Funding

Keywords

ASJC Scopus subject areas

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