501034-84-0Relevant academic research and scientific papers
Regio- and Stereoselective Copper(II)-Catalyzed Hydrosilylation of Activated Allenes in Water: Access to Vinylsilanes
Pashikanti, Srinath,Calderone, Joseph A.,Nguyen, Matthew K.,Sibley, Christopher D.,Santos, Webster L.
supporting information, p. 2443 - 2446 (2016/06/09)
By using catalytic amounts of copper(II), 4-picoline, and dimethylphenylsilylpinacol borane, a series of allenoates were silylated on the β carbon in good to excellent yields and high (E)-selectivity. The mild and efficient silylation method is conducted in water under atmospheric conditions to afford vinylsilanes.
Synthesis of 1,4-enamino ketones by [3,3]-rearrangements of dialkenylhydroxylamines
Pecak, Wiktoria H.,Son, Jongwoo,Burnstine, Amy J.,Anderson, Laura L.
supporting information, p. 3440 - 3443 (2014/07/21)
The synthesis of 1,4-enamino ketones has been achieved through the [3,3]-rearrangement of dialkenylhydroxylamines generated from the addition of N-alkenylnitrones to electron-deficient allenes. The mild conditions required for this reaction, and the simultaneous installation of a fluorenyl imine N-protecting group as a consequence of the rearrangement, avoid spontaneous cyclization of the 1,4-enamino ketones to form the corresponding pyrroles and allow for the isolation and controlled divergent functionalization of these reactive intermediates. The optimization, scope, and tolerance of the new method are discussed with demonstrations of the utility of the products for the synthesis of pyrroles, 1,4-diones, and furans.
Solvent-Controlled Bifurcated Cascade Process for the Selective Preparation of Dihydrocarbazoles or Dihydropyridoindoles
Mo, Dong-Liang,Wink, Donald J.,Anderson, Laura L.
supporting information, p. 13217 - 13225 (2016/02/19)
A solvent-controlled cascade process has been identified for the dual purpose of the preparation of either dihydrocarbazoles or dihydropyridoindoles from identical N-aryl-α,β-unsaturated nitrones and electron-deficient allene starting materials. These reactions proceed smoothly under mild metal-free conditions affording a range of two types of skeletally distinct indole-based heterocycles in high yield and diastereoselectivity. These transformations demonstrate the use of a bifurcated cascade process that hinges on the ring-opening event of a benzazepine intermediate for the synthesis of skeletally diverse heterocyclic products and rapid access to biologically-significant, indole-based structures.
Thermal decomposition of triphenylphosphonium alkyl ester salts
Castaneda, Fernando,Aliaga, Christian,Acuna, Cristina,Silva, Paul,Bunton, Clifford A.
experimental part, p. 1188 - 1208 (2009/04/16)
In thermolyses of molten triphenylphosphonium alkyl ester bromides and chlorides, alkyl = methyl, ethyl, isopropyl, at 130 and 225°C, initial attack of the halide ion on the methyl group gives the methyl halide and ylid 1, Ph3P = CH2, which can be methylated, or is protonated by the phosphonium salt with transylidation giving Ph3P+-CH3X-, X = Br, Cl. The initial reactions of the ethyl or isopropyl esters are with the halide ion, X-, as a base giving ylid, 1, which can be protonated by HX or by transylidation. The t-butyl ester generates Ph3P+-CH3X-but no products of transylidation. The first-formed ylid1, can be trapped by reactive alkyl and acyl halides, and the transient ylidic esters decompose thermally to triphenyl phosphine oxide, Ph3P = O, react further with unreacted phosphonium ester, or are trapped by added aldehyde in a Wittig reaction. The final product compositions are affected by a decrease in pressure, due to escape of volatile intermediates, and by replacement of the X- halide ion by the less nucleophilic and basic tosylate ion. Reactions under reflux, in solution in chloroform, or in suspension in benzene, are similar to those of the molten salts, but yields are generally lower at the lower temperatures. Copyright Taylor & Francis Group, LLC.
