30780-45-1Relevant articles and documents
Intermolecular C-O Bond Formation with Alkoxyl Radicals: Photoredox-Catalyzed α-Alkoxylation of Carbonyl Compounds
Banoun, Camille,Bourdreux, Flavien,Magnier, Emmanuel,Dagousset, Guillaume
supporting information, p. 8926 - 8930 (2021/11/17)
Due to the high reactivity of alkoxyl (RO·) radicals and their propensity to easily undergo β-scission or Hydrogen Atom Transfer (HAT) reactions, intermolecular alkoxylations involving RO· radicals are barely described. We report herein for the first time the efficient intermolecular trapping of alkoxyl radicals by silyl enol ethers. This photoredox-mediated protocol enables the introduction of both structurally simple and more complex alkoxy groups into a wide range of ketones and amides.
Highly efficient synthesis of functionalized α-oxyketones: Via Weinreb amides homologation with α-oxygenated organolithiums
Pace, Vittorio,Murgia, Irene,Westermayer, Sophie,Langer, Thierry,Holzer, Wolfgang
supporting information, p. 7584 - 7587 (2016/07/06)
An efficient, chemoselective homologation of Weinreb amides to the corresponding variously substituted α-oxyketones has been developed via the addition of lithiated α-oxygenated species. This one-step, experimentally easy, high yielding protocol is amenable not only for accessing simple α-oxyketones but also for more complex substituted ones ranging from primary and secondary alkyl-type to aromatic ones. Full delivery of the stereochemical information contained in the starting materials is observed through both the employment of enantioenriched Weinreb amides and optically active organolithium species.
Experimental study on the reaction pathway of α-haloacetophenones with NaOMe: Examination of bifurcation mechanism
Tagawa, Kohei,Sasagawa, Keita,Wakisaka, Ken,Monjiyama, Shunsuke,Katayama, Mika,Yamataka, Hiroshi
, p. 119 - 126 (2014/02/14)
The reaction of PhCOCH2Br and NaOMe in MeOH gave PhCOCH 2OH as the major product and PhCOCH2OMe as the minor product. Substituent effects on the reactivity and product selectivity revealed that an electron-withdrawing substituent on the phenyl ring enhanced the overall reactivity and gave more alcohol than ether. It was indicated that the alcohol was formed via carbonyl addition-epoxidation, whereas the ether was formed by direct substitution. Substituent effects on the reaction rates, as well as the effects of NaOMe concentration on the rate and product ratio for both reactions of PhCOCH2Br and PhCOCH2CI are in line with the mechanism that the alcohol and ether products were formed via two independent and concurrent routes, carbonyl addition and a-carbon attack, respectively, and thus the reaction mechanism could be different from the bifurcation mechanism previously predicted for the reaction of PhCOCH2Br by a simulation study in the gas phase.