14189-85-6Relevant articles and documents
Mechanistic Perspectives in the Regioselective Indole Addition to Unsymmetrical Silyloxyallyl Cations
Bresnahan, Caitlin G.,Taylor-Edinbyrd, Kiara A.,Cleveland, Alexander H.,Malone, Joshua A.,Dange, Nitin S.,Milet, Anne,Kumar, Revati,Kartika, Rendy
, p. 7166 - 7174 (2019)
Our investigations on the reaction mechanism to account for regioselectivity on the addition of indoles to unsymmetrical silyloxyallyl cations are reported. Using both experimental and computational methods, we confirmed the significance of steric effects from the silyl ether group toward directing the inward approach of indoles, leading to nucleophilic attack at the less substituted electrophilic α′-carbon. The role of residual water toward accelerating the rate of reaction is established through stabilization of the participating silyloxyallyl cation.
Cooperative benzylic-oxyallylic stabilized cations: regioselective construction of α-quaternary centers in ketone-derived compounds
Dange, Nitin S.,Stepherson, Jacob R.,Ayala, Caitlan E.,Fronczek, Frank R.,Kartika, Rendy
, p. 6312 - 6319 (2015)
We describe a novel reactivity of benzylic-stabilized oxyallyl cations towards regioselective construction of carbon quaternary centers. These synthetically useful intermediates were readily generated upon ionization of aryl substituted α-hydroxy methylenol ethers with catalytic, mild Bronsted acid. The emerging unsymmetrical oxyallyl cations were then directly captured by indoles and other nucleophiles with exquisite control of regioselectivity, predictably at the electrophilic carbon bearing the alkyl substituent to produce highly functionalized, value-added enol ethers.
Chemistry of Singlet Oxygen. 53. Environmental Effects on the Photooxygenation of 2-Methoxy-3-methyl-2-cyclopenten-1-one
Kwon, Byoung-Mog,Foote, Christopher S.
, p. 3878 - 3882 (2007/10/02)
Photooxygenation of 2-methoxy-3-methyl-2-cyclopenten-1-one (1) gives both ene and dioxetane products.The product distribution depends on temperature and solvent.In CD3OD, the photooxygenation of 1 gives solvent adducts as initial products, and the ratio of stereoisomers is very sensitive to the amount of CD3OD in the reaction mixture.The results are discussed in terms of possible intermediates for the ene and dioxetane products, especially an exciplex.
