Dialkyl Dicyanofumarates as Oxidizing Reagents for the Conversion of Thiols into Disulfides and Selenols into Diselenides. Issue 46 (5th September 2017)

• Record Type: Journal Article
• Authors: Mlostoń, Grzegorz; Capperucci, Antonella; Tanini, Damiano; Hamera‐Fałdyga, Róża; Heimgartner, Heinz
• Is Part Of: European journal of organic chemistry. Issue 46(2017)
• Page Start: 6831
• Page End: 6839
• Publication Date: 2017-09-05
• Subjects: Disulfides -- Diselenides -- Oxidation -- Electron transfer -- Michael addition; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201701066
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract : Aliphatic and aromatic thiols react smoothly with dialkyl dicyanofumarates in CH2 Cl2 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. Abstract : Dialkyl dicyanofumarates act as efficient hydrogen acceptors towards diverse thiols and selenols to yield the desired disulfides and diselenides, respectively. In most cases, the yields are high to excellent. The only side‐products are isomeric dicyanosuccinates formed in 1:1 ratios. A single‐electron transfer (SET) mechanism offers a likely explanation for the reaction course.