1092094-19-3Relevant articles and documents
Dichlorination of α-Diazo-β-dicarbonyls using (dichloroiodo)benzene
Coffey, Keith E.,Murphy, Graham K.
, p. 1003 - 1007 (2015)
Abstract α-Diazo-β-dicarbonyl compounds were chlorinated using (dichloro)iodobenzene and an activating catalyst. A broad range of reaction rates was observed, which paralleled the relative stability/nucleo-philicity of the diazo compounds. Acyclic diazocarbonyls reacted faster than cyclics, and β-diketones were much faster to react than β-keto esters or β-diesters. Lewis acid activation was used for the first time, allowing us to overcome instances of poor chemoselectivity. Though the yields ranged from low to good, this chlorination reaction has again proven a mild and effective halogenation strategy.
Geminal Dichlorination of Phenyliodonium Ylides of β-Dicarbonyl Compounds through Double Ligand Transfer from (Dichloroiodo)benzene
Tao, Jason,Tuck, Tina N.,Murphy, Graham K.
, p. 772 - 782 (2016/03/01)
Pre-formed phenyliodonium ylides of cyclic and acyclic β-diketones, β-keto esters and β-diesters were reacted with (dichloroiodo)benzene, resulting in transfer of both chloride ligands onto the ylidic carbon. These two hypervalent iodine(III) compounds exhibit high reactivity towards each other under mild reaction conditions and typically afford the gem-dichloride products in good yield. Upon comparison of these chlorination reactions with those of the analogous diazocarbonyl compounds, reactions of iodonium ylides were unilaterally faster, and often gave the products in higher yield.
A high performance oxidation method for secondary alcohols by inductive activation of TEMPO in combination with pyridine-bromine complexes
Mei, Zhen-Wu,Omote, Takumi,Mansour, Mounir,Kawafuchi, Hiroyuki,Takaguchi, Yutaka,Jutand, Anny,Tsuboi, Sadao,Inokuchi, Tsutomu
experimental part, p. 10761 - 10766 (2009/04/11)
A new TEMPO-mediated catalytic oxidation method in combination with Py·HBr3 (stoichiometric) is developed for oxidation of secondary alcohols to the corresponding ketones. The performance of this oxidizing system is better compared with that of TEMPO method combined with R4NBr3. Poly(4-vinylpyridine)·HBr3 can be used in place of Py·HBr3. The electron-withdrawing substituent at the C-4 position of TEMPO increases the reactivity of TEMPO significantly in the oxidation of electron-deficient alcohols such as polyhaloalkylmethanols. Inductive effect of the substituent of TEMPO is discussed through the characterization of the redox potential of N-O radical by cyclic voltammetry.
