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Dialkyl Dicyanofumarates as Oxidizing Reagents for the Conversion of Thiols into Disulfides and Selenols into Diselenides
Author(s) -
Mlostoń Grzegorz,
Capperucci Antonella,
Tanini Damiano,
HameraFałdyga Róża,
Heimgartner Heinz
Publication year - 2017
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201701066
Subject(s) - chemistry , reagent , amine gas treating , moiety , oxidizing agent , cysteamine , diastereomer , primary (astronomy) , organic chemistry , carbon disulfide , disulfide bond , enamine , transamination , thiol , polymer chemistry , medicinal chemistry , combinatorial chemistry , catalysis , biochemistry , physics , astronomy , enzyme
Aliphatic and aromatic thiols react smoothly with dialkyl dicyanofumarates in CH 2 Cl 2 at room temperature to give the corresponding disulfides in excellent yields. Aliphatic 1,2‐, 1,3‐, and 1,4‐dithiols afford cyclic disulfides. Analogous reaction courses were observed for selenols, and the required diselenides also formed in nearly quantitative yields. In all of the reactions, dialkyl dicyanosuccinates formed as 1:1 mixtures of diastereoisomers as the only other product. Cysteamine (2‐mercaptoethylamine) behaved differently; the Michael addition of the primary amine group led to the complete consumption of the dicyanofumarate, and the formation of the disulfide containing an enamine moiety occurred without the formation of dicyanosuccinate.