Aminotetrazole Synthesis from Secondary Amides by C–C Bond Nitrogenation

Abstract

The development of novel methods for the preparation of aminotetrazoles is of long-standing interest to chemists due to the great importance of these compounds in chemistry and biology. Here, we report an efficient method for the preparation of aminotetrazoles from secondary amides by selective C–C bond cleavage. Compared with the conventional laborious and cumbersome approaches to aminotetrazoles, this chemistry provides a highly efficient nitrogenation strategy, with the installation of four nitrogen atoms into a secondary amide in one step.

Key words

aminotetrazoles - secondary amides - C–C bond cleavage - rearrangement - nitrogenation

• References and Notes

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• 17 Aminotetrazoles 2a–y; General ProcedureUnder air, the appropriate secondary amide 1 (0.3 mmol) was dissolved in TCE (1 mL, 0.3 M) and Tf₂O (169 mg, 0.6 mmol) was added at 0 °C. The mixture was stirred at 0 °C for 15 min, then TMSN₃ (104 mg, 0.9 mmol) was added and the mixture was warmed to 40 °C. The vial was sealed, and the mixture was stirred under air at 40 °C for 24 h then cooled to RT. The reaction was quenched with Et₃N (5 mL) at 0 °C, and the mixture was diluted with EtOAc (12 mL). The organic phase was filtered through a pad of silica gel using EtOAc to dilute the product. The filtrate was concentrated and the residue was purified by flash chromatography (silica gel). N-Methyl-1-phenyl-1H-tetrazol-5-amine (2a)Yellow solid; yield: 33.6 mg (64%). ¹H NMR (400 MHz, CDCl₃): δ = 7.53–7.47 (m, 2 H), 7.47–7.40 (m, 3 H), 4.86 (br s, 1 H), 3.06 (d, J = 4.8 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 155.29, 133.05, 130.06, 129.62, 123.80, 30.70. HRMS (ESI): m/z [M + H]⁺ calcd for C₈H₁₀N₅: 176.0931; found: 176.0935