797762-31-3Relevant academic research and scientific papers
The first samarium(II)-mediated aryl radical cyclisation onto an aromatic ring
Ohno, Hiroaki,Iwasaki, Hiroki,Eguchi, Toru,Tanaka, Tetsuaki
, p. 2228 - 2229 (2004)
Intramolecular arylation of aryl radicals was mediated by SmI 2/HMPA in the presence of i-PrOH to give spirocycles and/or reduced cine-cyclised products, while the reaction in the absence of i-PrOH gave the rearomatised fused rings.
Hydroarylation of Arenes via Reductive Radical-Polar Crossover
Flynn, Autumn R.,Mcdaniel, Kelly A.,Hughes, Meredith E.,Vogt, David B.,Jui, Nathan T.
supporting information, p. 9163 - 9168 (2020/07/10)
A photocatalytic system for the dearomative hydroarylation of benzene derivatives has been developed. Using a combination of an organic photoredox catalyst and an amine reductant, this process operates through a reductive radical-polar crossover mechanism where aryl halide reduction triggers a regioselective radical cyclization event, followed by anion formation and quenching to produce a range of complex spirocyclic cyclohexadienes. This light-driven protocol functions at room temperature in a green solvent system (aq. MeCN) without the need for precious metal-based catalysts or reagents or the generation of stoichiometric metal byproducts.
Functionalization and rearrangement of spirocyclohexadienyl oxindoles: Experimental and theoretical investigations
Rousseau, Geraldine,Robert, Frederic,Landais, Yannick
experimental part, p. 11160 - 11173 (2010/05/02)
The preparation and functionalization of spirocyclohexa-2,5diene oxindoles is described. The spirocyclic core of the title compounds was installed by using a SmI2-mediated cyclization of aryl iodobenzamides. Epoxidation with CF3COsu
Rearrangement of spirocyclic oxindoles with lithium amide bases
Rousseau, Geraldine,Robert, Frederic,Schenk, Kurt,Landais, Yannick
supporting information; experimental part, p. 4441 - 4444 (2009/05/07)
(Chemical Equation Presented) Spirocyclohexa-2,5-dienes were shown to rearrange at -40 °C, when treated with 1 equiv of LDA. Alkyl halides and aldehydes then reacted with the resulting phenanthridinone lithium enolate intermediates, with distinct regioselectivities and high diastereocontrol, to afford functionalized dearomatized phenanthridinones which were elaborated further. A mechanistic scheme involving a diisopropylamine-mediated proton transfer was proposed to rationalize the rearrangement.
Samarium(II)-mediated spirocyclization by intramolecular aryl radical addition onto an aromatic ring
Iwasaki, Hiroki,Eguchi, Toru,Tsutsui, Nozomi,Ohno, Hiroaki,Tanaka, Tetsuaki
experimental part, p. 7145 - 7152 (2009/05/07)
(Chemical Equation Presented) Samarium(II)-mediated spirocyclization by intramolecular addition of aryl radicals onto an aromatic ring was achieved by the reaction of N-(2-iodophenyl)-N-alkylbenzamides with SmI2 in the presence of HMPA, yielding spirocyclic indolin-2-one derivatives. The ether congeners afford spirocyclic benzofuran derivatives in moderate yields by aryl radical addition onto a benzene ring without having an electron-withdrawing group. The reaction with other aryl groups such as naphthalene and indole rings is also described.
