DBDMH-Promoted Methylthiolation in DMSO: A Metal-Free Protocol to Methyl Sulfur Compounds with Multifunctional Groups

Abstract

Organic thioethers play an important role in the discovery of drugs and natural products. However, the green synthesis of organic sulfide compounds remains a challenging task. The convenient and efficient synthesis of 5-alkoxy-3-halo-4-methylthio-2(5H)-furanones from DMSO is performed via the mediation of 1,3-dibromo-5,5-dimethylhydantoin (DBDMH), affording a facile route for the sulfur-functionalization of 3,4-dihalo-2(5H)-furanones under transition metal-free conditions. This new approach has demonstrated the functionalization of non-aromatic Csp2-X-type halides with unique structures containing C-X, C-O, C=O and C=C bonds. Compared with traditional synthesis methods using transition metal catalysts with ligands, this reaction has many advantages, such as the lower temperature, the shorter reaction time, the wide substrate range and good functional group tolerance. Notably, DMSO plays multiple roles, and is simultaneously used as an odorless methylthiolating reagent and safe solvent.

Transition‐metal‐free Cyclization of Mucohalic Acids with Sulfonyl Hydrazides: An Approach to Pyridazin‐3(2H)‐ones

“…These results indicate that the reaction might not undergo via a radical pathway. Thus, based on the results presented above and our previous works on the chemistry of mucohalic acids, [21,[30][31][32][33]47] a possible mechanism is proposed for the model reaction, which is shown as Scheme 5. Initially, mucobromic acid 2 a is isomerized into the ring-opened form 2 a'.…”