Thiourea-Catalyzed C−F Bond Activation: Amination of Benzylic Fluorides

Camille Houle; Paul R. Savoie; Clotilde Davies; Damien Jardel; Pier Alexandre Champagne; Brigitte Bibal; Jean François Paquin

doi:10.1002/chem.202001905

Thiourea-Catalyzed C−F Bond Activation: Amination of Benzylic Fluorides

Camille Houle, Paul R. Savoie, Clotilde Davies, Damien Jardel, Pier Alexandre Champagne, Brigitte Bibal, Jean François Paquin

Chemistry and Environmental Science

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

13 Scopus citations

Abstract

We describe the first thiourea-catalyzed C−F bond activation. The use of a thiourea catalyst and Ti(OiPr)₄ as a fluoride scavenger allows the amination of benzylic fluorides to proceed in moderate to excellent yields. Preliminary results with S- and O-based nucleophiles are also presented. DFT calculations reveal the importance of hydrogen bonds between the catalyst and the fluorine atom of the substrate to lower the activation energy during the transition state.

Original language	English (US)
Pages (from-to)	10620-10625
Number of pages	6
Journal	Chemistry - A European Journal
Volume	26
Issue number	46
DOIs	https://doi.org/10.1002/chem.202001905
State	Published - Aug 17 2020

All Science Journal Classification (ASJC) codes

Catalysis
Organic Chemistry

Keywords

C−F activation
benzyl amines
benzyl fluorides
organocatalysis
thiourea

Access to Document

10.1002/chem.202001905

Cite this

@article{beb9690f798d42a8bc319187e66c59af,

title = "Thiourea-Catalyzed C−F Bond Activation: Amination of Benzylic Fluorides",

abstract = "We describe the first thiourea-catalyzed C−F bond activation. The use of a thiourea catalyst and Ti(OiPr)4 as a fluoride scavenger allows the amination of benzylic fluorides to proceed in moderate to excellent yields. Preliminary results with S- and O-based nucleophiles are also presented. DFT calculations reveal the importance of hydrogen bonds between the catalyst and the fluorine atom of the substrate to lower the activation energy during the transition state.",

keywords = "C−F activation, benzyl amines, benzyl fluorides, organocatalysis, thiourea",

author = "Camille Houle and Savoie, {Paul R.} and Clotilde Davies and Damien Jardel and Champagne, {Pier Alexandre} and Brigitte Bibal and Paquin, {Jean Fran{\c c}ois}",

note = "Publisher Copyright: {\textcopyright} 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2020",

month = aug,

day = "17",

doi = "10.1002/chem.202001905",

language = "English (US)",

volume = "26",

pages = "10620--10625",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "Wiley-VCH Verlag",

number = "46",

}

TY - JOUR

T1 - Thiourea-Catalyzed C−F Bond Activation

T2 - Amination of Benzylic Fluorides

AU - Houle, Camille

AU - Savoie, Paul R.

AU - Davies, Clotilde

AU - Jardel, Damien

AU - Champagne, Pier Alexandre

AU - Bibal, Brigitte

AU - Paquin, Jean François

PY - 2020/8/17

Y1 - 2020/8/17

N2 - We describe the first thiourea-catalyzed C−F bond activation. The use of a thiourea catalyst and Ti(OiPr)4 as a fluoride scavenger allows the amination of benzylic fluorides to proceed in moderate to excellent yields. Preliminary results with S- and O-based nucleophiles are also presented. DFT calculations reveal the importance of hydrogen bonds between the catalyst and the fluorine atom of the substrate to lower the activation energy during the transition state.

AB - We describe the first thiourea-catalyzed C−F bond activation. The use of a thiourea catalyst and Ti(OiPr)4 as a fluoride scavenger allows the amination of benzylic fluorides to proceed in moderate to excellent yields. Preliminary results with S- and O-based nucleophiles are also presented. DFT calculations reveal the importance of hydrogen bonds between the catalyst and the fluorine atom of the substrate to lower the activation energy during the transition state.

KW - C−F activation

KW - benzyl amines

KW - benzyl fluorides

KW - organocatalysis

KW - thiourea

UR - http://www.scopus.com/inward/record.url?scp=85088168149&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85088168149&partnerID=8YFLogxK

U2 - 10.1002/chem.202001905

DO - 10.1002/chem.202001905

M3 - Article

C2 - 32315102

AN - SCOPUS:85088168149

SN - 0947-6539

VL - 26

SP - 10620

EP - 10625

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 46

ER -

Thiourea-Catalyzed C−F Bond Activation: Amination of Benzylic Fluorides

Abstract

All Science Journal Classification (ASJC) codes

Keywords

Access to Document

Other files and links

Fingerprint

Cite this