221626-12-6Relevant articles and documents
Iron-Nickel Dual-Catalysis: A New Engine for Olefin Functionalization and the Formation of Quaternary Centers
Green, Samantha A.,Vásquez-Céspedes, Suhelen,Shenvi, Ryan A.
supporting information, p. 11317 - 11324 (2018/09/18)
Alkene hydroarylation forms carbon-carbon bonds between two foundational building blocks of organic chemistry: olefins and aromatic rings. In the absence of electronic bias or directing groups, only the Friedel-Crafts reaction allows arenes to engage alkenes with Markovnikov selectivity to generate quaternary carbons. However, the intermediacy of carbocations precludes the use of electron-deficient arenes, including Lewis basic heterocycles. Here we report a highly Markovnikov-selective, dual-catalytic olefin hydroarylation that tolerates arenes and heteroarenes of any electronic character. Hydrogen atom transfer controls the formation of branched products and arene halogenation specifies attachment points on the aromatic ring. Mono-, di-, tri-, and tetra-substituted alkenes yield Markovnikov products including quaternary carbons within nonstrained rings.
Silicates as Latent Alkyl Radical Precursors: Visible-Light Photocatalytic Oxidation of Hypervalent Bis-Catecholato Silicon Compounds
Corcé, Vincent,Chamoreau, Lise-Marie,Derat, Etienne,Goddard, Jean-Philippe,Ollivier, Cyril,Fensterbank, Louis
, p. 11414 - 11418 (2015/10/12)
This works introduces hypervalent bis-catecholato silicon compounds as versatile sources of alkyl radicals upon visible-light photocatalysis. Using Ir[(dF(CF3)ppy)2(bpy)](PF6) (dF(CF3)ppy=2-(2,4-difluorophenyl)-5-trifluoromethylpyridine, bpy=bipyridine) as catalytic photooxidant, a series of alkyl radicals, including highly reactive primary ones can be generated and engaged in various intermolecular homolytic reactions. Based on cyclic voltammetry, Stern-Volmer studies, and supported by calculations, a mechanism involving a single-electron transfer from the silicate to the photoactivated iridium complex has been proposed. This oxidative photocatalyzed process can be efficiently merged with nickel-catalyzed Csp2-Csp3 cross-coupling reactions.
Cross-coupling reactions through the intramolecular activation of Alkyl(triorgano)silanes
Nakao, Yoshiaki,Takeda, Masahide,Matsumoto, Takuya,Hiyama, Tamejiro
supporting information; scheme or table, p. 4447 - 4450 (2010/08/19)
(Figure Presented) Cross-Si-ing the Jordan: Cross-coupling reactions of 2-(2-hydroxyprop-2-yl)phenylsubstituted alkylsilanes with a variety of aryl halides proceed in the presence of palladium and copper catalysts. The use of K3PO4 base allows for highly chemoselective alkyl coupling with both primary and secondary alkyl groups (Alk).
