15359-97-4Relevant articles and documents
Ab initio study of the selective alkylation of m-cresol with tert-butanol catalyzed by SO3H-functionalized ionic liquids
Zhou, Jinxia,Liu, Xiumei,Zhang, Shuguang,Mao, Jingbo,Guo, Xinwen
, p. 232 - 237 (2010)
Our previous work showed that for catalytic alkylation of m-cresol with tert-butanol (TBA) SO3H-functionalized ionic liquids exhibited several characteristic advantages over conventional catalysts. This work investigated the reaction mechanism of the alkylation of m-cresol with tert-butanol catalyzed by the SO3H-functionalized ionic liquid (IL) through quantum chemical calculation in combination with the experimental studies. The experimental results showed that 2-tert-butyl-5-methyl phenol (2-TBC), 4-tert-butyl-3-methyl phenol (4-TBC) and tert-butyl-m-cresol ether (TBMCE) products were all primary products, while 2,6-di-tert-butyl-3-methyl phenol (2,6-DTBC) was a secondary product. The calculation results indicated that the selectivities of the products depended on the fundamental natures of the reactive sites, including the orbital overlap, the Coulomb and the steric effect in the interaction between the tert-butyl ion ([t-C4H9]+) and the m-cresol; the TBMCE was dynamically favored but not thermodynamically stable, while the C-alkylated products, especially 2-TBC, were the thermodynamically preferred products; the IL played an important role in generating the [t-C4H9]+ from the TBA and the final products from the intermediates.
KOtBu: A Privileged Reagent for Electron Transfer Reactions?
Barham, Joshua P.,Coulthard, Graeme,Emery, Katie J.,Doni, Eswararao,Cumine, Florimond,Nocera, Giuseppe,John, Matthew P.,Berlouis, Leonard E. A.,McGuire, Thomas,Tuttle, Tell,Murphy, John A.
supporting information, p. 7402 - 7410 (2016/07/06)
Many recent studies have used KOtBu in organic reactions that involve single electron transfer; in the literature, the electron transfer is proposed to occur either directly from the metal alkoxide or indirectly, following reaction of the alkoxide with a solvent or additive. These reaction classes include coupling reactions of halobenzenes and arenes, reductive cleavages of dithianes, and SRN1 reactions. Direct electron transfer would imply that alkali metal alkoxides are willing partners in these electron transfer reactions, but the literature reports provide little or no experimental evidence for this. This paper examines each of these classes of reaction in turn, and contests the roles proposed for KOtBu; instead, it provides new mechanistic information that in each case supports the in situ formation of organic electron donors. We go on to show that direct electron transfer from KOtBu can however occur in appropriate cases, where the electron acceptor has a reduction potential near the oxidation potential of KOtBu, and the example that we use is CBr4. In this case, computational results support electrochemical data in backing a direct electron transfer reaction.
Mizoroki-heck-type reaction mediated by potassium tert-butoxide
Shirakawa, Eiji,Zhang, Xuejing,Hayashi, Tamio
supporting information; experimental part, p. 4671 - 4674 (2011/06/27)
In the absence of transition-metal catalysts, a Mizoroki-Heck-type reaction proceeded to give stilbene derivatives in a simple manner using an aryl halide, a styrene derivative, KOtBu, EtOH, and DMF (see scheme; DMF=N,N- dimethylformamide).
