Palladium-catalyzed benzylic arylation of N-benzylxanthone imine
(Chemical Equation Presented) The direct benzylic arylation of N-benzylxanthone imine with aryl chloride proceeds under palladium catalysis, yielding the corresponding coupling product. The product is readily transformed to benzhydrylamine. Taking into consideration that the imine is readily available from benzylic amine, the overall transformation represents a formal cross-coupling reaction of aryl halide with α-aminobenzyl metal.
Niwa, Takashi,Yorimitsu, Hideki,Oshima, Koichiro
supporting information; experimental part
p. 4689 - 4691
(2009/05/13)
Organic Reactive Intermediates: Part IX-Radical Ions as Reactive Intermediates in Redox Reactions of Triphenylphosphazines
Two representative phosphazines namely, fluorenylidenetriphenylphosphazine (1) and diphenylmethylenetriphenylphosphazine (2) are shown to undergo oxidation and reduction involving single electron transfer to yield the corresponding cation and anion radicals, respectively.These ion radicals are unstable and decompose to give rise to a blend of other intermediates.Those which act almost certainly as principal intermediates in oxidation and reduction are carbenes and diazoalkane radical anions respectively.
Handoo, Kishan L.,Gadru, Kanchan
p. 412 - 417
(2007/10/02)
The Electrochemical Reduction of Fluorenone Tosylhydrazone: Evidence Consistent with Formation of the Tosyl Nitrene Anion Radical
Fluorenone tosylhydrazone (Fl=NNHTs) undergoes one-electron reductive dehydrogenation in DMF-0.1 F (n-Bu)4NClO4 to give hydrogen and its conjugate base Fl=NN-Ts as products.Fl=NN-Ts is subsequently reduced at more negative potential to a dianion radical (Fl=NNTs dianion radical) that is stable on the cyclic voltammetric time scale.On the coulometric time scale or in the presence of added proton donors (pKa ca.29), Fl=NNTs dianion radical decomposes to give FlHNH2 and TsNH2 as the principal products.A pathway is proposed for the reaction of Fl=NNTs dianion radical which involves rate-determining proton abstraction by the nitrogen atom α to the fluorene moiety.Cyclic voltammetric and chronoamperometric data are presented which are consistent with the formation of the tosyl nitrene anion radical as a short-lived, unobserved intermediate.
Galen, Dean A. Van,Barnes, James H.,Hawley, M. Dale
p. 2544 - 2550
(2007/10/02)
Transaminations Using 9-Fluorenone-1-carboxylic Acid