We retro-synthetically derive γ-functional ITLs from functional glycidols following a concise three-step synthetic route (Figure ). As functional glycidols are prominent reagents for anionic polymerization and epoxy resins, they are commercially available in a wide variety, rendering this synthetic route an attractive strategy. The first reaction involves the transformation of the functional glycidyl ether 1 to the corresponding thiirane 2. Following a procedure by Endo et al, the formation of poly(episulfide)s was successfully avoided by using 2,3-butanediol as solvent. An initial attempt to use glycidol for this reaction, however, resulted in various side-products and low thiirane yields (26%), presumably due to the interfering free alcohol group (ESI, section 1.3.1 and Figure ,S43). Consequently, tert-butyl glycidyl ether 1a was used as precursor giving thiirane 2a in 90% yield (Figure -3). The subsequent synthetic steps are carried out in one pot and comprise a thiirane ring-opening followed by the final cyclization. As such, 2a was alkylated using lithium acetonitrile to give the corresponding mercaptonitrile through ring-opening of the thiirane (Figure ). This intermediate was then treated with concentrated hydrochloric acid to undergo tert-butyl deprotection and cyclization simultaneously, delivering γhydroxymethyl ITL 3a in 83% yield. 1 H NMR spectroscopy of 3a revealed a very characteristic chemical shift (δ = 12.21 ppm) for the iminium proton signal (Figure ). In the previously published work by Goff et al, the authors assigned these protons to a broad triplet at δ = 7.40 ppm instead. Supportive to our assignment, we isolated an unknown precipitate during a recrystallization attempt of 3a. Its 1 H NMR spectrum showed only this triplet at δ = 7.40 ppm with a unique J-coupling constant of 50.9 Hz (Figure ), the latter which had been previously reported for J14 NH coupling of ammonium ions. We therefore hypothesized that the iminium group can undergo spontaneous hydrolysis to release ammonium chloride (see outlined mechanism in the ESI, Figure ); this had been previously observed for imidates and amidines, too. Through a comparison between FT-IR spectra of this unknown precipitate and commercially available ammonium chloride, our supposition was con-firmed as both spectra were identical (Figure ). Successful crystallization and single crystal X-ray diffraction experiments confirmed the general structure of 3a with respect to its configuration and protonation state (Figure ). The packaging unit consists of four chiral molecules in a 1/1 R/S ratio with the chloride anion stabilized by two =NH + 2 and one hydroxyl group via hydrogen bonding (Figure , Figure ). Further information on data collection and refinement of the crystal structure are given as ESI (Table ).