New Approach to the Synthesis of Strained Cyclic Systems: I. Iminocyclobutenes and Iminothietanes from 1,3-Dilithio-3-phenylpropyne and Methyl Isothiocyanate

Abstract

The reaction of 1,3-dilithio-3-phenylpropyne with methyl isothiocyanate in THF-hexane at -90 to -55°C, followed by successive treatment of intermediate product with a donor of protons, superbase, and alkyl halide, yields isomeric iminocyclobutenes and iminothietanes in addition to the expected aminothiophene. The ratio of the products depends on the amount and nature of proton donor (MeOH, t-BuOH), base (MeONa, t-BuOM, M = Li, Na, K; t-AmOK), co-solvent (DMSO, HMPA), and alkyl halide (MeI, EtI, BuBr). The system t-BuOH(MeOH)-t-BuOK-DMSO is the most favorable for the formation of the corresponding iminocyclobutene.