Hexacarbonylmolybdenum(0)-Induced Dechalcogenization of Allylic Sulfides, Sulfones, and Selenides: Nucleophilic Substitution and Reductive Dechalcogenization

• Published in: Bulletin of the Chemical Society of Japan Vol. 62; no. 9; pp. 2913 - 2918
• Main Authors: Masuyama, Yoshiro, Yamada, Kohji, Shimizu, Soh-hei, Kurusu, Yasuhiko
• Format: Journal Article
• Language: English
• Published: Tokyo The Chemical Society of Japan 01.09.1989; Chemical Society of Japan
• Subjects: Chemistry; Exact sciences and technology; Organic chemistry; Chemical reduction; Organic selenide; Desulfurization; Aliphatic compound; Transition metal Carbonyl; Nucleophilic substitution; Desulfonylation; Allylic compound; Organic sulfide
• ISSN: 0009-2673; 1348-0634
• DOI: 10.1246/bcsj.62.2913

Hexacarbonylmolybdenum(0)-induced dechalcogenization of allylic sulfides I, sulfones II, and selenides III in refluxing dioxane, which led to nucleophilic substitutions with carbon nucleophiles. Attack of the relatively bulky nucleophile, 2-ethoxycarbonyl-2-sodiocyclopentanone occurred regioselectively at the less substituted end of the allyl unit after the dechalcogenization to give only one isomer. Attack of diethyl sodiomalonate to I and III occurred preferentially at γ-position, and that to II occurred preferentially at the more substituted end of the allyl unit after the desulfonylation. In the absence of the carbon nucleophiles, treatment of I, II, and III with Mo(CO)6 in refluxing dioxane caused reductive dechalcogenization. Addition of H2O accelerated the reductive dechalcogenization.