Salt‐Free CatAnionic Vesicular Nanoreactor from Dithiocarbamate: Michael Addition of Nitroolefins in Water

The salt‐free CatAnionic vesicle is previously generated by mixing cationic and anionic amphiphiles and removing the salt that occurred as a byproduct from the mixture. In this study, a new strategy to produce the salt‐free CatAnionic vesicle of N , N ‐dialkylammonium N , N ‐dialkyldithiocarbamate (AmDTC) is reported through a one‐step condensation between secondary amine and CS 2 . The AmDTC dispersed in water, resulting in the spontaneous formation of salt‐free CatAnionic vesicles. Among several AmDTCs, the N , N ‐didodecylammonium N , N ‐didodecyldithiocarbamate ( AmDTC‐C12 ) showed high stability and is applied as a vesicular nanoreactor for the Michael addition in water. These vesicles catalyzed aqueous Michael additions of nitroolefins, affording 23 adducts in 65%–92% yields. The vesicles enabled preparative‐scale and one‐pot Michael addition by in situ generation of AmDTC‐C12 vesicle afforded the Michael adducts also in good yields. The AmDTC‐C12 vesicular nanoreactor is applied for the synthesis of (±)‐baclofen with 54% yields over three steps. Reusability of the AmDTC‐C12 is demonstrated and allowed the reuse up to seven cycles. Finally, chemical recycling of N , N ‐didodecylamine precursor is demonstrated by converting AmDTC‐C12 to N , N ‐didodecylammonium chloride salt by simple acidification. Owing to their simple precursors and mild synthesis, salt‐free CatAnionic vesicles from AmDTC show promising and untapped potentials as organocatalysts and delivery applications.