Some Practical Methods for the Application of 5-Metallo-1-benzyl-1H-tetrazoles in Synthesis

Abstract

Nucleophilic reagents such as 5-lithiotetrazoles are synthetically powerful tools for the installation of tetrazole functional groups, but they are of limited utility due to the instability of tetrazole-derived carbanions. Herein, we report practical methods for the generation and use of new 5-metallo-1-benzyl-1H-tetrazoles (M = K, MgX, ZnX) derived from either 1-benzyl-1H-tetrazole or 1-benzyl-5-bromo-1H-tetrazole. By varying the metal counterion, the tetrazole carbanion stability was improved. Potassium- and magnesium-derived reagents underwent additions to carbonyl ­compounds at –30 and –20 °C, respectively. The isolated yields (41–85%) from these and other reactions were comparable to those reported for 5-lithiotetrazoles at much lower temperatures (–78 to –98 °C).

Key words

nucleophilic addition - Grignard reaction - metalation - tetrazoles - counterion effects

• References and Notes

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