Mechanochemical Synthesis of Trifluoromethyl Arenes: Nanocellulose-Supported Deaminative Trifluoromethylation of Aromatic Amines

Satenik Mkrtchyan; Vishal B. Purohit; Oleksandr Shalimov; Jiří Zapletal; Sehrish Sarfaraz; Khurshid Ayub; Juraj Filo; Mika Sillanpää; Marek Skoršepa; Viktor O. Iaroshenko

doi:10.1021/acssuschemeng.4c00846

Mechanochemical Synthesis of Trifluoromethyl Arenes: Nanocellulose-Supported Deaminative Trifluoromethylation of Aromatic Amines

Satenik Mkrtchyan, Vishal B. Purohit, Oleksandr Shalimov, Jiří Zapletal, Sehrish Sarfaraz, Khurshid Ayub, Juraj Filo, Mika Sillanpää, Marek Skoršepa, Viktor O. Iaroshenko

Chemical Engineering Technology

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

2 Citations (Scopus)

Abstract

A convenient one-pot procedure for the mechanochemical nanocellulose-supported synthesis of trifluoromethyl arenes has been developed through the selective transformation of an aromatic amino group into the trifluoromethyl functionality using pyrylium tetrafluoroborate (Pyry-BF₄) and trifluoromethyltrimethylsilane (TMSCF₃) via in situ formation of the pyridinium salt intermediate under transition metal-free conditions. The nanocellulose acts here as a green reaction medium, and the reaction does not occur without this additive. The scope of the present protocol includes synthesis of 28 trifluoromethyl arenes in excellent yields via a selective (ipso-)substitution (S_NAr) of aromatic amino group with CF₃ functionality. This method could have a great significance in pharmaceutical industries for the late-stage functionalization of active pharmaceutical ingredients (APIs)/drugs.

Original language	English
Pages (from-to)	8980-8989
Number of pages	10
Journal	ACS Sustainable Chemistry and Engineering
Volume	12
Issue number	24
DOIs	https://doi.org/10.1021/acssuschemeng.4c00846
Publication status	Published - 17 Jun 2024

Keywords

Mechanochemistry
Metal-free
Nanocellulose
Solvent-free
Sustainability
Trifluoromethylation

ASJC Scopus subject areas

General Chemistry
Environmental Chemistry
General Chemical Engineering
Renewable Energy, Sustainability and the Environment

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10.1021/acssuschemeng.4c00846

Cite this

Mkrtchyan, S., Purohit, V. B., Shalimov, O., Zapletal, J., Sarfaraz, S., Ayub, K., Filo, J., Sillanpää, M., Skoršepa, M., & Iaroshenko, V. O. (2024). Mechanochemical Synthesis of Trifluoromethyl Arenes: Nanocellulose-Supported Deaminative Trifluoromethylation of Aromatic Amines. ACS Sustainable Chemistry and Engineering, 12(24), 8980-8989. https://doi.org/10.1021/acssuschemeng.4c00846

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abstract = "A convenient one-pot procedure for the mechanochemical nanocellulose-supported synthesis of trifluoromethyl arenes has been developed through the selective transformation of an aromatic amino group into the trifluoromethyl functionality using pyrylium tetrafluoroborate (Pyry-BF4) and trifluoromethyltrimethylsilane (TMSCF3) via in situ formation of the pyridinium salt intermediate under transition metal-free conditions. The nanocellulose acts here as a green reaction medium, and the reaction does not occur without this additive. The scope of the present protocol includes synthesis of 28 trifluoromethyl arenes in excellent yields via a selective (ipso-)substitution (SNAr) of aromatic amino group with CF3 functionality. This method could have a great significance in pharmaceutical industries for the late-stage functionalization of active pharmaceutical ingredients (APIs)/drugs.",

keywords = "Mechanochemistry, Metal-free, Nanocellulose, Solvent-free, Sustainability, Trifluoromethylation",

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Mkrtchyan, S, Purohit, VB, Shalimov, O, Zapletal, J, Sarfaraz, S, Ayub, K, Filo, J, Sillanpää, M, Skoršepa, M & Iaroshenko, VO 2024, 'Mechanochemical Synthesis of Trifluoromethyl Arenes: Nanocellulose-Supported Deaminative Trifluoromethylation of Aromatic Amines', ACS Sustainable Chemistry and Engineering, vol. 12, no. 24, pp. 8980-8989. https://doi.org/10.1021/acssuschemeng.4c00846

TY - JOUR

T1 - Mechanochemical Synthesis of Trifluoromethyl Arenes

T2 - Nanocellulose-Supported Deaminative Trifluoromethylation of Aromatic Amines

AU - Mkrtchyan, Satenik

AU - Purohit, Vishal B.

AU - Shalimov, Oleksandr

AU - Zapletal, Jiří

AU - Sarfaraz, Sehrish

AU - Ayub, Khurshid

AU - Filo, Juraj

AU - Sillanpää, Mika

AU - Skoršepa, Marek

AU - Iaroshenko, Viktor O.

PY - 2024/6/17

Y1 - 2024/6/17

N2 - A convenient one-pot procedure for the mechanochemical nanocellulose-supported synthesis of trifluoromethyl arenes has been developed through the selective transformation of an aromatic amino group into the trifluoromethyl functionality using pyrylium tetrafluoroborate (Pyry-BF4) and trifluoromethyltrimethylsilane (TMSCF3) via in situ formation of the pyridinium salt intermediate under transition metal-free conditions. The nanocellulose acts here as a green reaction medium, and the reaction does not occur without this additive. The scope of the present protocol includes synthesis of 28 trifluoromethyl arenes in excellent yields via a selective (ipso-)substitution (SNAr) of aromatic amino group with CF3 functionality. This method could have a great significance in pharmaceutical industries for the late-stage functionalization of active pharmaceutical ingredients (APIs)/drugs.

AB - A convenient one-pot procedure for the mechanochemical nanocellulose-supported synthesis of trifluoromethyl arenes has been developed through the selective transformation of an aromatic amino group into the trifluoromethyl functionality using pyrylium tetrafluoroborate (Pyry-BF4) and trifluoromethyltrimethylsilane (TMSCF3) via in situ formation of the pyridinium salt intermediate under transition metal-free conditions. The nanocellulose acts here as a green reaction medium, and the reaction does not occur without this additive. The scope of the present protocol includes synthesis of 28 trifluoromethyl arenes in excellent yields via a selective (ipso-)substitution (SNAr) of aromatic amino group with CF3 functionality. This method could have a great significance in pharmaceutical industries for the late-stage functionalization of active pharmaceutical ingredients (APIs)/drugs.

KW - Mechanochemistry

KW - Metal-free

KW - Nanocellulose

KW - Solvent-free

KW - Sustainability

KW - Trifluoromethylation

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JF - ACS Sustainable Chemistry and Engineering

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ER -

Mechanochemical Synthesis of Trifluoromethyl Arenes: Nanocellulose-Supported Deaminative Trifluoromethylation of Aromatic Amines

Abstract

Keywords

ASJC Scopus subject areas

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