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Alpha-lithiation of n-alkyl groups in pyrazoles
Journal article   Peer reviewed

Alpha-lithiation of n-alkyl groups in pyrazoles

Alan R. Katritzky, Chandra Jayaram and Vassilatos N. Socrates
Tetrahedron, Vol.39(12), pp.2023-2029
1983

Abstract

1,3,5-Trimethylpyrazole and l-ethyl-3,5-dimethylpyrazole undergo lithiation exclusively at the α -position of the N-alkyl group. 1-Benzylpyrazole is metallated under kinetic control at -78° at the CH 2 group, but the metallorganic intermediate rearranges rapidly at 23° to give the thermodynamically more stable 5-lithio-l-benzylpyrazole. 1-Methylpyrazole gives mixtures of α- and 5-lithiation; 1-ethylpyrazole showed only 5-lithiation. The carbanions were trapped by a variety of electrophiles.

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