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A new efficient and general synthetic methodology to access γ-aminothiols was investigated and developed. 1,3-Thiazines were used as convenient precursors and were prepared by a fast microwave-assisted three-component reaction (3CR) of thioamides, aldehydes, and alkenes. The transformation of thiazines into aminothiols was achieved via a thiazinium salt hydrolysis, in three very facile steps.