Facile synthesis of 1,5-disubstituted tetrazoles by reacting a ruthenium acetylide complex with trimethylsilyl azide

Abstract

Treatment of [Ru]–CCPh (1, [Ru] = (η⁵-C₅H₅)(dppe)Ru, dppe = Ph₂PCH₂CH₂PPh₂) with trimethylsilyl azide afforded the cationic nitrile complex {[Ru]NCCH₂Ph}[N₃] (2) and the further cycloaddition of 2 with trimethylsilyl azide at 60 °C afforded the N(2)-bound tetrazolato complex [Ru]N₄CCH₂Ph (3). The regiospecific alkylation of 3 gave a series of cationic N(2)-bound N(4)-alkylated-5-benzyl tetrazolato complexes {[Ru]N₄(CH₂R)CCH₂Ph}[Br] (4a, R = C₆F₅; 4b, R = Ph; 4c, R = 4-CN-C₆H₄; 4d, R = 2,6-F₂-C₆H₃; 4e, R = 6-CH₂Br-C₅NH₃) and the subsequent cleavage of the Ru–N bond of 4a–4e gave N(1)-alkylated-5-benzyl tetrazoles N₄(CH₂R)CCH₂Ph (5a–5e) in good to excellent yields and [Ru]–Br, which, on reacting with phenylacetylene, resulted in the formation of 1 thus forming a reaction cycle. The structures of 2, 3, 4a, 4c and 5a were confirmed by single-crystal X-ray diffraction analysis.