Enabling nucleophilic substitution reactions of activated alkyl fluorides through hydrogen bonding

Pier Alexandre Champagne; Julien Pomarole; Marie Ève Thérien; Yasmine Benhassine; Samuel Beaulieu; Claude Y. Legault; Jean François Paquin

doi:10.1021/ol400765a

Enabling nucleophilic substitution reactions of activated alkyl fluorides through hydrogen bonding

Pier Alexandre Champagne, Julien Pomarole, Marie Ève Thérien, Yasmine Benhassine, Samuel Beaulieu, Claude Y. Legault, Jean François Paquin

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

80 Scopus citations

Abstract

It was discovered that the presence of water as a cosolvent enables the reaction of activated alkyl fluorides for bimolecular nucleophilic substitution reactions. DFT calculations show that activation proceeds through stabilization of the transition structure by a stronger F···H ₂O interaction and diminishing C-F bond elongation, and not simple transition state electrostatic stabilization. Overall, the findings put forward a distinct strategy for C-F bond activation through H-bonding.

Original language	English (US)
Pages (from-to)	2210-2213
Number of pages	4
Journal	Organic Letters
Volume	15
Issue number	9
DOIs	https://doi.org/10.1021/ol400765a
State	Published - May 3 2013
Externally published	Yes

All Science Journal Classification (ASJC) codes

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry

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10.1021/ol400765a

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abstract = "It was discovered that the presence of water as a cosolvent enables the reaction of activated alkyl fluorides for bimolecular nucleophilic substitution reactions. DFT calculations show that activation proceeds through stabilization of the transition structure by a stronger F···H 2O interaction and diminishing C-F bond elongation, and not simple transition state electrostatic stabilization. Overall, the findings put forward a distinct strategy for C-F bond activation through H-bonding.",

author = "Champagne, {Pier Alexandre} and Julien Pomarole and Th{\'e}rien, {Marie {\`E}ve} and Yasmine Benhassine and Samuel Beaulieu and Legault, {Claude Y.} and Paquin, {Jean Fran{\c c}ois}",

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AU - Champagne, Pier Alexandre

AU - Pomarole, Julien

AU - Thérien, Marie Ève

AU - Benhassine, Yasmine

AU - Beaulieu, Samuel

AU - Legault, Claude Y.

AU - Paquin, Jean François

PY - 2013/5/3

Y1 - 2013/5/3

N2 - It was discovered that the presence of water as a cosolvent enables the reaction of activated alkyl fluorides for bimolecular nucleophilic substitution reactions. DFT calculations show that activation proceeds through stabilization of the transition structure by a stronger F···H 2O interaction and diminishing C-F bond elongation, and not simple transition state electrostatic stabilization. Overall, the findings put forward a distinct strategy for C-F bond activation through H-bonding.

AB - It was discovered that the presence of water as a cosolvent enables the reaction of activated alkyl fluorides for bimolecular nucleophilic substitution reactions. DFT calculations show that activation proceeds through stabilization of the transition structure by a stronger F···H 2O interaction and diminishing C-F bond elongation, and not simple transition state electrostatic stabilization. Overall, the findings put forward a distinct strategy for C-F bond activation through H-bonding.

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DO - 10.1021/ol400765a

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JO - Organic Letters

JF - Organic Letters

IS - 9

ER -

Enabling nucleophilic substitution reactions of activated alkyl fluorides through hydrogen bonding

Abstract

All Science Journal Classification (ASJC) codes

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