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

84 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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UR - https://www.scopus.com/pages/publications/84877136020#tab=citedBy

U2 - 10.1021/ol400765a

DO - 10.1021/ol400765a

M3 - Article

C2 - 23614350

AN - SCOPUS:84877136020

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SP - 2210

EP - 2213

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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