19164-60-4Relevant academic research and scientific papers
Manganese-Catalyzed Electrochemical Deconstructive Chlorination of Cycloalkanols via Alkoxy Radicals
Allen, Benjamin D. W.,Hareram, Mishra Deepak,Seastram, Alex C.,McBride, Tom,Wirth, Thomas,Browne, Duncan L.,Morrill, Louis C.
supporting information, p. 9241 - 9246 (2019/11/19)
A manganese-catalyzed electrochemical deconstructive chlorination of cycloalkanols has been developed. This electrochemical method provides access to alkoxy radicals from alcohols and exhibits a broad substrate scope, with various cyclopropanols and cyclobutanols converted into synthetically useful β- and γ-chlorinated ketones (40 examples). Furthermore, the combination of recirculating flow electrochemistry and continuous inline purification was employed to access products on a gram scale.
Facile o-quinodimethane formation from benzocyclobutenes triggered by the Staudinger reaction at ambient temperature
Kohyama, Aki,Koresawa, Eri,Tsuge, Kiyoshi,Matsuya, Yuji
supporting information, p. 6205 - 6208 (2019/06/07)
Electron-donating iminophosphoranes were found to significantly enhance 4π-ring opening of benzocyclobutenes to generate o-quinodimethanes at 20-25 °C. These iminophosphorane benzocyclobutenes can be conveniently generated from azide benzocyclobutenes and phosphines via the Staudinger reaction. Thus, Staudinger reaction-triggered sequential molecular transformations of the azide benzocyclobutenes have been established via o-quinodimethanes at ambient temperature, which is expected to exhibit potential for a wide range of applications.
Mechanistic Study on Thermal Isomerization of 1-Methylbenzocyclobutenol to 2-Methylacetophenone
Iida, Katsumi,Komada, Kaori,Saito, Masaichi,Yoshioka, Michikazu
, p. 7407 - 7411 (2007/10/03)
Heating 1-trideuteriomethylbenzocyclobutenol 7 in benzene-d6 at 160°C gave 2-monodeuteriomethyl- and 2-methylacetophenone 9 and 10 in a ratio of 96:4. Thermolysis of 7 in nonpolar solvents (hexane, toluene, mesitylene) gave similar results. On the contrary, heating 7 in polar solvents (ethanol, acetonitrile, chloroform) or in benzene-d6 in the presence of proton source (PhCO2H) gave 10 as the major product. However, heating a mixture of 7 and N-phenylmaleimide at 160°C in benzene-d6 or acetonitrile-d3 gave adduct 12 of N-phenylmaleimide and the dienol generated by ring opening of 7 almost quantitatively. These results indicate that 1-methylbenzocyclobutenol undergoes selective thermal opening to the E-dienol. The resulting E-dienol isomerizes to 2-methylacetophenone by 1,5-sigmatropic shift of hydrogen from the methyl group in nonpolar solvent. In polar solvent, the E-dienol isomerizes to 2-methylacetophenone by both intra- and intermolecular processes. The kH/kD value for isomerization was 1.13. Since this relatively low value is a secondary kinetic effect, overall reaction is governed by the ring opening step. The selective opening to the E-dienol was supported by calculation.
DECOMPOSITION ACIDO-CATALYSEE D'AZIDES TERTIAIRES BENZOCYCLOBUTENIQUES. NOUVELLE METHODE DE SYNTHESE DU NOYAU INDOLIQUE PAR EXTENSION DU CYCLE
Adam, G.,Andrieux, J.,Plat, M
, p. 399 - 408 (2007/10/02)
Treatment of benzocyclobutenols substituted on the functional carbon by the HN3/BF3-Et2O reagent allows the synthesis to the corresponding tertiary azides.The latter by acid-catalysed breakdown, lead to 2-substituted indoles.A similar result is obtained by treating directly the alcohols with hydrazoic acid and concentrated sulfuric acid.This new route to indole nucleus is also extended to the synthesis of policyclic indoles.
SYNTHESIS OF NATURAL PRODUCTS VIA TERTIARY AZIDES. II. 2-ALKYL AND 2-ARYL INDOLES.
Adam, Gerard,Andrieux, Jean,Plat, Michel
, p. 3181 - 3184 (2007/10/02)
A new route to indoles: the acid-catalysed breakdown of 1-azido 1,2-dihydrobenzocyclobutenes.
