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.