F:Flammable;557-40-4Relevant articles and documents
Furukawa et al.
, p. 3149 (1973)
Clean protocol for deoxygenation of epoxides to alkenes: Via catalytic hydrogenation using gold
Fiorio, Jhonatan L.,Rossi, Liane M.
, p. 312 - 318 (2021/01/29)
The epoxidation of olefin as a strategy to protect carbon-carbon double bonds is a well-known procedure in organic synthesis, however the reverse reaction, deprotection/deoxygenation of epoxides is much less developed, despite its potential utility for the synthesis of substituted olefins. Here, we disclose a clean protocol for the selective deprotection of epoxides, by combining commercially available organophosphorus ligands and gold nanoparticles (Au NP). Besides being successfully applied in the deoxygenation of epoxides, the discovered catalytic system also enables the selective reduction N-oxides and sulfoxides using molecular hydrogen as reductant. The Au NP catalyst combined with triethylphosphite P(OEt)3 is remarkably more reactive than solely Au NPs. The method is not only a complementary Au-catalyzed reductive reaction under mild conditions, but also an effective procedure for selective reductions of a wide range of valuable molecules that would be either synthetically inconvenient or even difficult to access by alternative synthetic protocols or by using classical transition metal catalysts. This journal is
Versatile etherification of alcohols with allyl alcohol by a titanium oxide-supported molybdenum oxide catalyst: Gradual generation from titanium oxide and molybdenum oxide
Kon, Yoshihiro,Fujitani, Tadahiro,Nakashima, Takuya,Murayama, Toru,Ueda, Wataru
, p. 4618 - 4625 (2018/09/29)
Etherification using allyl alcohol to produce allyl ether via dehydration is a fundamental technique for producing fine chemicals that can be applied to electronic devices. We demonstrate a sustainable method to synthesize allyl ethers from allyl alcohol with various alcohols up to a 91% yield, with water as the sole by-product. In this reaction, the active catalyst is gradually generated as the reaction proceeds through the simple mixing of TiO2 and MoO3. The dispersion of MoO3 on the spent catalyst has been observed by XRD, HAADF-STEM, and STEM-EDS mapping. This catalyst shows excellent catalytic activity by virtue of the highly dispersed nature of MoO3 supported on TiO2, which is reusable at least five times. According to a mechanistic study including the measurement of XPS of MoO3 on TiO2 and control experiments using SiO2 and Al2O3 supports, the suitable reducibility of MoO3 to coordinate the allyl moiety on TiO2 seems to be a key factor for high-yielding syntheses of various allyl ethers even under heterogeneous reaction conditions. The reaction mechanism is considered to be as follows: σ-allyl species are formed from dehydration of the allyl alcohol, followed by a nucleophilic attack by another alcohol against the σ-allyl carbon to give allyl ethers. The developed catalytic system should be suitable for easily handled syntheses of allyl ethers due to the employment of commercially available MoO3 and TiO2 with halide- and organic solvent-free reaction conditions.
