Sultines (cyclic sulfinate esters) are largely unexplored class of compounds, even though they have been known since late 19th century, which is mostly attributed to difficult and wasteful synthesis. For the past 20 years, research into novel synthetic methods has not ceased, since sultines are potentially versatile building blocks for preparation of biologically active molecules as they undergo ring opening, alkylation, reduction and oxidation reactions yielding variety of useful products. [1,2] Experimental research yielded new synthetic method for γ-sultine synthesis through trimethylenemethane intermediates reaction with sulfur dioxide. Optimization of reaction conditions and catalytical system allowed yields up to 82% of various γ-sultines. Further investigation into synthetic utility of the obtained products uncovered possibility to practically “regenerate” trimethylenemethane from these γ-sultines and sequentially form adduct to aniline. Additionally, ring opening reactions with carbon nucleophiles were performed achieving various sulfoxides with allyl alcohol moiety.