81395-26-8Relevant articles and documents
Reductive Etherification of Aldehydes and Ketones with Alcohols and Triethylsilane Catalysed by Yb(OTf)3: an Efficient One-Pot Benzylation of Alcohols
Pelosi, Azzurra,Lanari, Daniela,Temperini, Andrea,Curini, Massimo,Rosati, Ornelio
supporting information, p. 4527 - 4539 (2019/08/26)
The one-pot synthesis of symmetrical and unsymmetrical ethers from aldehydes and ketones can be conveniently performed using Yb(OTf)3 as catalyst and triethylsilane as reducing agent in presence of alcohols. This methodology leads to the synthesis of ether derivatives with good yields. Notably, this process resulted a useful tool to protect alcohols as benzyl ether derivatives using differently substituted benzaldehydes as protecting agents under mild conditions. A plausible mechanism was also proposed. (Figure presented.).
Radical substitution with azide: TMSN3-PhI(OAc)2 as a substitute of in3
Pedersen, Christian Marcus,Marinescu, Lavinia Georgeta,Bols, Mikael
, p. 816 - 822 (2007/10/03)
TMSN3 and PhI(OAc)2 were found to promote high-yield azide substitution of ethers, aldehydes and benzal acetals. The reaction is fast and occurs at zero to ambient temperature in acetonitrile. However, it is essential for the reaction that TMSN3 is added subsequent to the mixture of PhI(OAc)2 and the substrate. A primary deuterium kinetic isotope effect was found for the azidonation of benzyl ethers both with TMSN3-PhI(OAc)2 and with IN3. Also a Hammett free energy relationship study of this reaction showed good correlation with σ+ constants giving with ρ-values of -0.47 for TMSN 3-PhI(OAc)2 and -0.39 for IN3. On this basis a radical mechanism of the reaction was proposed. The Rayal Society of Chemistry 2005.
Skeletal Rearrangements on Chemical Ionization of Dibenzyl Ether and Derivatives
Kingston, Eric E.,Shannon, James S.,Diakiw, Vladimir,Lacey, Michael J.
, p. 428 - 440 (2007/10/02)
Protonated molecular ions of dibenzyl ether, formed by chemical ionization using hydrogen and isobutane as reagent gases, undergo skeletal rearrangements to lose water and formaldehyde, both in the ion source and the flight path.The rearrangements have been elucidated by deuterium labelling and chemical substitution.The water lost contains the reagent proton and an aromatic hydrogen atom, and the aromatic hydrogen atoms have been shown to be mobile prior to the reaction.It is proposed that the skeletal rearrangement for water loss is initiated by protonation on the other oxygen atom, followed by benzyl migration.The formaldehyde loss contains benzylic hydrogen atoms exclusively, and it is proposed that the skeletal rearrangement is preceded by hydrogen rearrangement of an oxygen protonated molecular ion to a ring protonated molecular ion.Daughter ion structures are supported by comparisons of their collision induced dissociation spectra with those of isomeric ions prepared by alternative routes.
