Selective Buchwald–Hartwig arylation ofC-amino-1,2,4-triazoles and other coordinating aminoheterocycles enabled by bulky NHC ligands and TPEDO activator

Selective Buchwald–Hartwig arylation ofC-amino-1,2,4-triazoles and other coordinating aminoheterocycles enabled by bulky NHC ligands and TPEDO activator Full article

Journal

Inorganic chemistry frontiers
ISSN: 2052-1553 , E-ISSN: 2052-1545

Output data

Year: 2023, Volume: 10, Number: 1, Pages: 218-239 Pages count : 22 DOI: 10.1039/d2qi01832b

Authors

Astakhov Alexander V. ¹ , Chernenko Andrey Yu. ¹ , Kutyrev Vadim V. ¹ , Ranny Gleb S. ¹ , Minyaev Mikhail E. ² , Chernyshev Victor M. ¹ , Ananikov Valentine P. ^1,2

Affiliations

1	Platov South-Russian State Polytechnic University, (NPI), Prosvescheniya st., 132, Novocherkassk, 346428, Russia
2	Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47, Moscow, 119991, Russia

C-Amino-1,2,4-triazoles are challenging polynitrogen substrates for metal-catalyzed arylation due to their multidentate character, enhanced coordinating ability and decreased nucleophilicity of the amino group. In the present study, the Buchwald–Hartwig cross-coupling of diverse 3(5)-amino-1,2,4-triazoles with aryl chlorides and bromides delivering (hetero)arylamino-1,2,4-triazoles in good-to-excellent yields under Pd/NHC catalysis was developed. The use of Pd complexes with bulky NHC ligands such as IPr*OMe and TPEDO (1,1,2,2-tetraphenylethane-1,2-diol) as an in situ Pd(II) to Pd(0) reductant enabled the selective arylation of the NH2 group even in acidic NH unprotected substrates and deactivated 1-substituted 5-amino- and 4-substituted 3-amino-1,2,4-triazoles. The reaction mechanism and structure–activity relationships were studied with DFT calculations. A significant effect of the position of the N-substituent in the 1,2,4-triazole ring on the favorable reaction pathways was revealed.

Astakhov A.V. , Chernenko A.Y. , Kutyrev V.V. , Ranny G.S. , Minyaev M.E. , Chernyshev V.M. , Ananikov V.P.
Selective Buchwald–Hartwig arylation ofC-amino-1,2,4-triazoles and other coordinating aminoheterocycles enabled by bulky NHC ligands and TPEDO activator
Inorganic chemistry frontiers. 2023. V.10. N1. P.218-239. DOI: 10.1039/d2qi01832b WOS Scopus OpenAlex

Web of science:	WOS:000889767900001
Scopus:	2-s2.0-85142719053
OpenAlex:	W4310580684

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Scopus	6
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