Nitroalkanes as Ketone Synthetic Equivalents in C–N and C–S Bond Formation Reactions

The umpolung strategy has been explored with 2-nitropropane
derivatives
featuring stabilized carbanion to latent ketone equivalents. The consequence
of changing intrinsic polarity at the α-carbon of nitroalkanes
induces simultaneous installation of the C–N bond at the geminal
and C–S bond at the vicinal positions of the nitro functionality.
Although the vicinal position of nitroalkanes bears poor electronic
bias, the latent ketone formation facilitates C–S bond formation
in the dithiole-3-thione core structure. The application of this methodology
is also demonstrated with the synthesis of amino derivatives of isothiazole-3-thione.