868765-12-2Relevant articles and documents
Light-Enabled Radical 1,4-Aryl Migration Via a Phospho-Smiles Rearrangement
De Abreu, Maxime,Belmont, Philippe,Brachet, Etienne
, p. 3758 - 3767 (2021/02/01)
Rearrangement reactions in organic chemistry are attractive strategies to build efficiently complex scaffolds, in just one step, from simple starting materials. Among them, aryl migrations are certainly one of the most useful and straightforward rearrangement for building attractive carbon-carbon bonds. Of note, anionic aryl migration reactions have been largely described compared to their radical counterparts. Recently, visible-light catalysis has proven its efficiency to generate such radical rearrangements due to the concomitant loss of a particle (often CO2 or SO2), which is the driving-force of the reaction. Here, we disclose a Smiles-type rearrangement, triggered by a phosphorus-containing unit (arylphosphoramidate), therefore called "phospho-Smiles"rearrangement, allowing a Csp2-Csp2 bond formation thanks to a 1,4-aryl migration reaction. In addition, combining this approach with a radical hydroamination/amination reaction produces an amination/phospho-Smiles cascade particularly attractive, for instance, to investigate the synthesis of the phthalazine core, a scarcely described scaffold of interest for medicinal chemistry projects.
Transition-metal-free oxidative cyclization reaction of enynals to access pyrane-2-one derivatives
Abbasi Kejani, Alireza,Ansari, Farzaneh,Armaghan, Mahsa,Balalaie, Saeed,Frank, Walter,Jafarpour, Farnaz,Khosravi, Hormoz
, p. 4263 - 4267 (2021/05/31)
A novel and efficient metal-free C-H functionalization of enynals is developed to synthesize α-pyrone derivatives via the formation of two C-O bonds. In this project, K2S2O8 has been introduced as an efficient oxygen source and C-H functionalization agent in regioselective oxidative cyclization reaction with a relatively broad substrate scope.
Synthesis of cyclopentaquinolinone and cyclopentapyridinone from: Ortho-alkynyl-N-arylaldehyde via superbase-promoted C-N, C-O and C-C bond formation
Saini, Kapil Mohan,Saunthwal, Rakesh K.,Sushmita,Verma, Akhilesh K.
supporting information, p. 5594 - 5601 (2020/08/21)
An environmentally benign, transition metal-free, superbase-mediated intramolecular annulation of o-alkynylaldehydes with primary amines forms highly functionalized amino-substituted cyclopentaquinolinones and cyclopentapyridinones via C-N, C-C, and CO bond formation. Contrary to the traditional approaches of ring closures, a different mode of annulation is disclosed. The protocol involves the in situ generations of imine intermediate followed by potassium hydroxide-promoted intramolecular cyclization and subsequent dimethyl sulfoxide induced dehydrogenation leads to the formation of N-heterocycles. X-ray crystallographic studies support the assigned structures of the amino-fused N-heterocycles.
