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

16 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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title = "Mechanochemical Synthesis of Trifluoromethyl Arenes: Nanocellulose-Supported Deaminative Trifluoromethylation of Aromatic Amines",

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

UR - https://www.scopus.com/pages/publications/85195781881

U2 - 10.1021/acssuschemeng.4c00846

DO - 10.1021/acssuschemeng.4c00846

M3 - Article

AN - SCOPUS:85195781881

SN - 2168-0485

VL - 12

SP - 8980

EP - 8989

JO - ACS Sustainable Chemistry and Engineering

JF - ACS Sustainable Chemistry and Engineering

IS - 24

ER -

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

Abstract

Keywords

ASJC Scopus subject areas

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