title: Synthesis of Thioethers by InI₃-Catalyzed Substitution of Siloxy Group Using Thiosilanes.
abstract: The substitution of a siloxy group using thiosilanes smoothly occurred in the presence of InI₃ catalyst to yield the corresponding thioethers. InI₃ was a specifically effective catalyst in this reaction system, while other typical Lewis acids such as BF₃⋅OEt₂, AlCl₃, and TiCl4were ineffective. Various silyl ethers such as primary alkyl, secondary alkyl, tertiary alkyl, allylic, benzylic, and propargylic types were applicable. In addition, bulky OSitBuMe₂ and OSiiPr₃ groups, other than the OSiMe₃ group, were successfully substituted. The substitution reaction of enantiopure secondary benzylic silyl ether yielded the corresponding racemic thioether product, which suggested that the reaction of tertiary alkyl, secondary alkyl, benzylic, and propargylic silyl ethers would proceed via a SN1 mechanism.
authors: Frontier Research Base for Global Young Researchers, Center for Open Innovation Research and Education(COiRE), Graduate School of Engineering, Osaka University, Osaka 565-0871, Japan. nishimoto@chem.eng.osaka-u.ac.jp.
authors: Yoshihiro
authors: Y
authors: Nishimoto
authors: Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Osaka 565-0871, Japan. ayaokita@chem.eng.osaka-u.ac.jp.
authors: Aya
authors: A
authors: Okita
authors: Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Osaka 565-0871, Japan. baba@chem.eng.osaka-u.ac.jp.
authors: Akio
authors: A
authors: Baba
authors: Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Osaka 565-0871, Japan. yasuda@chem.eng.osaka-u.ac.jp.
authors: Makoto
authors: M
authors: Yasuda
mesh_terms: D002384:Catalysis; D007204:Indium / Q000737:chemistry*; D007454:Iodides / Q000737:chemistry; D015394:Molecular Structure; D012821:Silanes / Q000737:chemistry*; D013237:Stereoisomerism; D013440:Sulfides / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D007454:Iodides; D012821:Silanes; D013440:Sulfides; D007204:Indium
keywords: indium; silyl ethers; thioethers; thiosilanes