946076-27-3Relevant academic research and scientific papers
Alkene Carboarylation through Catalyst-Free, Visible Light-Mediated Smiles Rearrangement
Whalley, David M.,Duong, Hung A.,Greaney, Michael F.
supporting information, p. 1927 - 1930 (2019/01/16)
A light-mediated Truce–Smiles arylative rearrangement is described that proceeds in the absence of any photocatalyst. The protocol creates two C?C bonds from simple starting materials, with the installation of an aryl ring and a difluoroacetate moiety across unactivated alkenes. The reaction proceeds via a radical mechanism, utilizing a light-mediated reduction of ethyl bromodifluoroacetate by N,N,N′,N′-tetramethylethylenediamine (TMEDA) to set up intermolecular addition to an unactivated alkene, followed by Truce–Smiles rearrangement.
Synthesis of substituted 3-arylpiperidines and 3-arylpyrrolidines by radical 1,4 and 1,2-aryl migrations
Gheorghe, Alexandru,Quiclet-Sire, Béatrice,Vila, Xavier,Zard, Samir Z.
, p. 7187 - 7212 (2008/02/07)
A route to 3-arylpiperidines and 3-arylpyrrolidines involving radical 1,4- and 1,2-aryl migrations has been explored. For the piperidines, the first route requires a xanthate addition to an N-allylarylsulfonamide, followed by acetylation and treatment with lauroyl peroxide to give the corresponding 1,4-aryl transfer product. This compound can be converted into the desired piperidine derivative following acidic hydrolysis. For the second approach to piperidines, addition of an α-keto xanthate to olefins of type 14 causes 1,2-aryl migration leading to an α,β-unsaturated ester, which can be converted into a piperidine by the action of ammonia or a primary amine and sodium cyanoborohydride. Substituted 3-arylpyrrolidines can be obtained by simply starting with an α-amido substituted xanthate.
