摘要： The application of Wolff rearrangement of the diazoketones derived from α-amino acids has been well documented.¹ It has been generally observed that if the rearrangement is performed in aqueous solution, homologated acid is the expected products, while if the reaction is run in methanol or ammonia, the corresponding homologated ester or amide will be obtained. In connection with other synthetic work, we unexpectedly observed that the Wolff rearrangement of diazoketone 1 in anhydrous methanol gave exclusively γ-lactam 3 in excellent yield.(Scheme 1) The formation of this intramolecular cyclization product was apparently due to the nucleophilic attack of the intermediate ketene 2 by the tosyl protected amino group. Although the solvent methanol can serve as nucleophile, the exclusive formation of γ-lactam indicates the intermolecular nucleophilic attack of the ketene intermediate 2 by methanol is not effective enough to compete with intramolecular nucleophilic attack by the tosyl protected amino group. This observation aroused our interest in the generality of this reaction and its potential as a novel method for the direct synthesis of γ-lactams. We report here the results of the investigation of Wolff rearrangement of several diazoketones derived from N-tosyl protected α-amino acids and β-amino acids.

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