65263-74-3Relevant articles and documents
Use of Dithiasuccinoyl-Caged Amines Enables COS/H2S Release Lacking Electrophilic Byproducts
Cerda, Matthew M.,Mancuso, Jenna L.,Mullen, Emma J.,Hendon, Christopher H.,Pluth, Michael D.
supporting information, p. 5374 - 5380 (2020/03/19)
The enzymatic conversion of carbonyl sulfide (COS) to hydrogen sulfide (H2S) by carbonic anhydrase has been used to develop self-immolating thiocarbamates as COS-based H2S donors to further elucidate the impact of reactive sulfur species in biology. The high modularity of this approach has provided a library of COS-based H2S donors that can be activated by specific stimuli. A common limitation, however, is that many such donors result in the formation of an electrophilic quinone methide byproduct during donor activation. As a mild alternative, we demonstrate here that dithiasuccinoyl groups can function as COS/H2S donor motifs, and that these groups release two equivalents of COS/H2S and uncage an amine payload under physiologically relevant conditions. Additionally, we demonstrate that COS/H2S release from this donor motif can be altered by electronic modulation and alkyl substitution. These insights are further supported by DFT investigations, which reveal that aryl and alkyl thiocarbamates release COS with significantly different activation energies.
Efficient Synthesis of 1,2,4-Dithiazolidine-3,5-diones (Dithiasuccinoyl-amines) and Observations on Formation of 1,2,4-Thiadiazolidine-3,5-diones by Related Chemistry
Slomczynska, Urszula,Barany, George
, p. 241 - 246 (2007/10/02)
An efficient synthesis of 1,2,4-dithiazolidine-3,5-diones (1) from chlorocarbonylsulfenyl chloride (3) plus O-dimethylaminoethyl-N-alkyl or aryl thiocarbamates (4) has been worked out.In this synthesis, 1,2,4-thiadiazolidine-3,5-diones (5) have been shown to arise as low-level-by-products, and experiments were conducted to elucidate the mechanism of the side reaction.N,N'-Dimethyl-1,2,4-thiadiazolidine-3,5-dione (5a) was prepared in one step from N,N'-dimethylurea plus 3, or from 4a plus one equivalent of sulfuryl chloride.A general route to 5 involved reaction ofequimolar amounts of isocyanates (6), isothiocyanates (7) and sulfuryl chloride followed by hydrolysis of intermediate 9.Heterocycles reported have been characterized by nmr, ir, uv, ms, and hplc.
