Efficient Synthesis of a New Family of 2,6-Disulfanyl-9-selenabicyclo[3.3.1]nonanes

• Main Authors: Maxim V. Musalov, Vladimir A. Potapov, Svetlana V. Amosova
• Format: Article
• Language: English
• Published: MDPI AG 2021-05-01
• Series: Molecules
• Subjects: 2,6-disulfanyl-9-selenabicyclo[3.3.1]nonanes; transannular addition; 9-selenabicyclo[3.3.1]nonane-2,6-dithiolate anion; isothiouronium salts; 2,6-dibromo-9-selenabicyclo[3.3.1]nonane; selenium dibromide
• Online Access: https://www.mdpi.com/1420-3049/26/10/2849

The efficient synthesis of a new family of 2,6-disulfanyl-9-selenabicyclo[3.3.1]nonanes in high yields has been developed based on 9-selenabicyclo[3.3.1]nonane-2,6-dithiolate anion generated from bis-isothiouronium salt of 2,6-dibromo-9-selenabicyclo[3.3.1]nonane. The derivatives of 2,6-disulfanyl-9-selenabicyclo[3.3.1]nonane containing alkyl, allyl and benzyl moieties have been prepared in 90–99% yields by nucleophilic substitution of 9-selenabicyclo[3.3.1]nonane-2,6-dithiolate anion with alkyl, allyl and benzyl halides. The reaction of nucleophilic addition of 9-selenabicyclo[3.3.1]nonane-2,6-dithiolate anion to alkyl propiolates afforded 2,6-di(vinylsulfanyl)-9-selenabicyclo[3.3.1]nonanes. The conditions for regio- and stereoselective addition of 9-selenabicyclo[3.3.1]nonane-2,6-dithiolate anion to a triple bond of alkyl propiolates have been found. To date, not a single representative of 2,6-disulfanyl-9-selenabicyclo[3.3.1]nonanes has been described in the literature.