56180-49-5Relevant articles and documents
Bis- N -heterocyclic carbene palladium(IV) tetrachloride complexes: Synthesis, reactivity, and mechanisms of direct chlorinations and oxidations of organic substrates
McCall, A. Scott,Wang, Hongwang,Desper, John M.,Kraft, Stefan
supporting information; experimental part, p. 1832 - 1848 (2011/04/15)
This Article describes the preparation and isolation of novel octahedral CH2-bridged bis-(N-heterocyclic carbene)palladium(IV) tetrachlorides of the general formula LPdIVCl4 [L = (NHC)CH 2(NHC)] from LPdIICl2 and Cl2. In intermolecular, nonchelation-controlled transformations LPdIVCl 4 reacted with alkenes and alkynes to 1,2-dichlorination adducts. Aromatic, benzylic, and aliphatic C-H bonds were converted into C-Cl bonds. Detailed mechanistic investigations in the dichlorinations of alkenes were conducted on the 18VE PdIV complex. Positive solvent effects as well as kinetic measurements probing the impact of cyclohexene and chloride concentrations on the rate of alkene chlorination support a PdIV-Cl ionization in the first step. Product stereochemistry and product distributions from various alkenes also support Cl+-transfer from the pentacoordinated PdIV-intermediate LPdIVCl 3+ to olefins. 1-Hexene/3-hexene competition experiments rule out both the formation of π-complexes along the reaction coordinate as well as in situ generated Cl2 from a reductive elimination process. Instead, a ligand-mediated direct Cl+-transfer from LPd IVCl3+ to the π-system is likely to occur. Similarly, C-H bond chlorinations proceed via an electrophilic process with in situ formed LPdIVCl3+. The presence of a large excess of added Cl- slows cyclohexene chlorination while the presence of stoichiometric amounts of chloride accelerates both PdIV-Cl ionization and Cl+-transfer from LPdIVCl3 +. 1H NMR titrations, T1 relaxation time measurements, binding isotherms, and Job plot analysis point to the formation of a trifurcated Cl-...H-C bond in the NHC-ligand periphery as a supramolecular cause for the accelerated chemical events involving the metal center.
Ipso-Chlorination of 4-Alkylphenols Ethers. A Novel Route to 4-Chlorocyclohexa-2,5-dienones.
Ferron, Bruno,Jacquesy, Jean-Claude,Jouannetaud, Marie-Paule,Karam, Omar,Coustard, Jean-Marie
, p. 2949 - 2952 (2007/10/02)
Selective chlorination of 4-alkylphenols ethers with SbF5/CH2Cl2 (CHCl3, CCl4) yields 4-chlorocyclohexa-2,5-dienones; no α-chlorination to a carbonyl group is observed in the reaction conditions.
Phenol-Dienone Rearrangement in the Chlorination of p-Cresol with t-Butyl Hypochlorite
Husain, Sajid,Kifayatullah, Mohd
, p. 711 - 714 (2007/10/02)
From the chlorination of p-cresol with t-butyl hypochloride (3 mol) in acetic acid five non-phenolic compounds have been isolated and identified as substituted 2,5-cyclohexadienones (I-V).The formation of these compounds has been explained in terms of phenol-dienone and dienone-phenol rearrangements. 2,6-Dichloro-4-(2-chloro-4-methylphenoxy)-4-methyl-2,5-cyclohexadienone is a condensation product of the intermediate chlorocresols and its mechanistic details have been discussed.