Application of Azide-Tetrazole Tautomerism and Arylsulfanyl Group Dance in the Synthesis of Thiosubstituted Tetrazoloquinazolines

Synthesis 2021
Andris Jeminejs, Svetlana Marija Goliškina, Irina Novosjolova, Dmitrijs Stepanovs, Ērika Bizdēna, Māris Turks

Nucleophilic aromatic substitution reaction between 4-aryl­thio-2-chloroquinazolines and NaN3 takes place with an unusual sulfanyl group dance and leads to the formation of 5-(arylthio)tetrazolo[1,5-c]-quinazolines, which do not form the azide tautomer and do not undergo CuAAC reactions with alkynes. On the other hand, 5-azidotetrazolo[1,5-a]quinazoline (formally described as 2,4-diazidoquinazoline) undergoes regioselective nucleophilic aromatic substitution with thiols at C5 and forms 5-(alkyl/arylthio)tetrazolo[1,5-a]quinazolines, the structure of which has been proved by X-ray crystallography. The latter exist in tautomeric equilibrium with their 2-azidoquinazoline form, which provides possibility for copper-catalyzed azide–alkyne 1,3-dipolar cyclo­addition reaction, leading to the 4-alkyl/arylthio-2-(1H-1,2,3-triazol-1-yl)quinazolines.

Keywords
quinazolines, nucleophilic aromatic substitution, azide-tetrazole equilibrium, thiols, azides, triazoles
DOI
10.1055/s-0040-1706568
Hyperlink
https://www.thieme-connect.com/products/ejournals/abstract/10.1055/s-0040-1706568

Jeminejs, A., Goliškina, S., Novosjolova, I., Stepanovs, D., Bizdēna, Ē., Turks, M. Application of Azide-Tetrazole Tautomerism and Arylsulfanyl Group Dance in the Synthesis of Thiosubstituted Tetrazoloquinazolines. Synthesis, 2021, Vol. 53, No. 8, pp.1443-1456. ISSN 0039-7881. e-ISSN 1437-210X. Available from: doi:10.1055/s-0040-1706568

Publication language
English (en)