A New Route to Polykis(dialkylamino)benzenes and -naphthalenes Based on Protodefluorination of Electron-Rich Fluoroaromatics: Anion Radicals of Arenes as a Simple and Effective Alternative to ‘Classical’ LAH-Based Systems

Сорокин, В. И.; Ozeryanskii, Valery A.; Бородкин, Г. С.

doi:10.1055/s-2005-921755

Cited by 2 publications

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“…Given the failure of the palladium-catalyzed methodology, we were required to use the lithiation and protodefluorination pathway outlined in Scheme , which was developed by Sorokin and co-workers to prepare a variety of such compounds with piperidine, pyrrolidine, dimethylamine, and dibutylamine as substrates. The 3,6-difluorinated compounds may be converted to the corresponding protio derivatives by reaction with sodium biphenylide; using this reaction sequence, we have synthesized the 1,4-difluorotetrakis(amino)benzene compounds 1 , 3 , and 5 and subsequently defluorinated them to yield the corresponding compounds 2 , 4 , and 6 (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

“…The first is the well-known Buchwald−Hartwig amination reaction, which involves the palladium-catalyzed coupling of an aryl halide with an amine. The second involves the protodefluorination of 1,2,4,5-tetrakis(amino)-3,6-difluorobenzene compounds, which are simply 1,2,4,5-tetrakis(amino)benzene compounds in which the hydrogen atoms on the central benzene ring have been replaced by fluorine atoms. This is a readily prepared class of compound, being synthesized by the nucleophilic attack of lithium amides on hexafluorobenzene .…”

Section: Introductionmentioning

confidence: 99%

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On the Causes of Potential Inversion in 1,2,4,5-Tetrakis(amino)benzenes

et al. 2010

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Three 3,6-difluoro-1,2,4,5-tetrakis(amino)benzene compounds, bearing dimethylamino (1), piperidin-1-yl (3), or morpholin-1-yl (5) substituents, have been synthesized and subsequently defluorinated to give the corresponding 1,2,4,5-tetrakis(amino)benzene compounds 2, 4, and 6; the crystal structures of compounds 1, 4, and 6 have been obtained. Cyclic voltammetry shows that all six compounds will lose two electrons to form dications, and the use of suitable oxidizing agents has allowed isolation and crystallographic characterization of the dications 2(2+) and 6(2+) (as [PF(6)](2) salts) and 4(2+) (as a [I(5)][I(3)] salt). The separation DeltaE between the loss of the first electron and the second varies between compounds, from 0.23 V in 1 to 0.01 V in 6. Electrochemical studies involving the use of the noncoordinating electrolyte [Bu(4)N][B{C(6)H(3)(CF(3))(2)}(4)] show that it is possible to increase this separation, stabilizing the intermediate monocationic phase, and this has allowed the isolation and crystallographic characterization of the radical salts 2[B{C(6)H(3)(CF(3))(2)}(4)] and 4[B{C(6)H(3)(CF(3))(2)}(4)], the first radical cations of this family to be isolated. DFT studies of the ion pairing between oxidized forms of 1 and 2 and anions imply that the location of the ion pairing is different in the two species.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%