Reductive Etherification via Anion-Binding Catalysis
Reductive condensations of alcohols with aldehydes/ketones to generate ethers are catalyzed by a readily accessible thiourea organocatalyst that operates in combination with HCl. 1,1,3,3-tetramethyldisiloxane serves as a convenient reducing reagent. This strategy is applicable to challenging substrate combinations and exhibits functional group tolerance. Competing reductive homocoupling of the carbonyl component is suppressed.
Zhao, Chenfei,Sojdak, Christopher A.,Myint, Wazo,Seidel, Daniel
supporting information
p. 10224 - 10227
(2017/08/10)
Radical substitution with azide: TMSN3-PhI(OAc)2 as a substitute of in3
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.
Pedersen, Christian Marcus,Marinescu, Lavinia Georgeta,Bols, Mikael
p. 816 - 822
(2007/10/03)
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