Reaction of alcohols and silyl ethers in the presence of an indium/silicon-based catalyst system: Deoxygenation and allyl substitution

Baba, Akio; Yasuda, Makoto; Nishimoto, Yoshihiro; Saito, Takahiro; Onishi, Yoshiyuki

doi:10.1351/pac200880050845

Pure Appl. Chem., 2008, Vol. 80, No. 5, pp. 845-854

http://dx.doi.org/10.1351/pac200880050845

Reaction of alcohols and silyl ethers in the presence of an indium/silicon-based catalyst system: Deoxygenation and allyl substitution

Akio Baba, Makoto Yasuda, Yoshihiro Nishimoto, Takahiro Saito and Yoshiyuki Onishi

Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan

Abstract: An In(III)/Si catalyst system effects the direct allyl substitution of alcohols and silyl ethers under mild conditions. A deoxygenation of alcohols is also promoted by InCl₃ catalyst. This method requires no pretreatment or protection of hydroxy groups or deprotection of siloxy groups. The completion of the catalytic allylation depends on the low oxophilicity and high halophilicity of In(III) halide species, and other representative Lewis acids such as AlCl₃ and BF₃ have no catalytic activity for the allylations. The oxophilicity and halophilicity are also demonstrated by NMR studies.