A Sm(II)-Mediated Cascade Approach to Dibenzoindolo[3,2-<i>b</i>]carbazoles: Synthesis and Evaluation

Levick, Matthew; Grace, Iain; Dai, Sheng-Yao; Kasch, Nicholas; Muryn, Christopher A.; Lambert, Colin J.; Turner, Michael L.; Procter, David J.

doi:10.1021/ol500841b

Cited by 40 publications

(22 citation statements)

References 49 publications

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“…Subsequently,e xpected quadruple C À Nb ond formations occurred to give 14 d and 14 j in 38 and 22 %y ield, respectively.I nc omparison with elegant yet burdensome construction of similar dibenzoindolo[3,2-b]carbazoles for OFET devices, [26,27] this overall transformation highlights the synthetic potential of our carbazole synthesis. Thep recursor bis(sulfone) 13 was obtained from ar ather small aromatic compound (12)i n8 9% yield.…”

Section: Methodsmentioning

confidence: 91%

Transition‐Metal‐Free Synthesis of Carbazoles and Indoles by an S_NAr‐Based “Aromatic Metamorphosis” of Thiaarenes

et al. 2015

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Section: Methodsmentioning

confidence: 91%

Transition‐Metal‐Free Synthesis of Carbazoles and Indoles by an S_NAr‐Based “Aromatic Metamorphosis” of Thiaarenes

et al. 2015

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“…Thep recursor bis(sulfone) 13 was obtained from ar ather small aromatic compound (12)i n8 9% yield. Subsequently,e xpected quadruple C À Nb ond formations occurred to give 14 d and 14 j in 38 and 22 %y ield, respectively.I nc omparison with elegant yet burdensome construction of similar dibenzoindolo[3,2-b]carbazoles for OFET devices, [26,27] this overall transformation highlights the synthetic potential of our carbazole synthesis. Figure 1shows the UV/visible and fluorescence spectra of 14 j in dichloromethane.…”

Section: Methodsmentioning

confidence: 91%

Transition‐Metal‐Free Synthesis of Carbazoles and Indoles by an S_NAr‐Based “Aromatic Metamorphosis” of Thiaarenes

et al. 2015

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Dibenzothiophene dioxides,w hich are readily prepared through oxidation of the parent dibenzothiophenes, undergo nucleophilic aromatic substitution with anilines intermolecularly and then intramolecularly to yield the corresponding carbazoles in as ingle operation. The "aromatic metamorphosis" of dibenzothiophenes into carbazoles does not require any heavy metals.This strategy is also applicable to the synthesis of indoles.S ince electron-deficient thiaarene dioxides exhibit interesting reactivity,which is not observed for that the corresponding electron-rich azaarenes,acombination of at hiaarene-dioxide-specific reaction with the S N Ar-based aromatic metamorphosis allows transition-metal-free construction of difficult-to-prepare carbazoles.Carbazoles represent an important class of heteroaromatic compounds,many of which find aw ide range of applications as biologically active agents in medicinal chemistry [1] and as hole-transport and light-emitting materials in organic electronics. [2] Fort he last two decades,t ransition-metal catalysis has been used for constructing ac arbazole skeleton by catalytic C À Nb ond formation, and includes Buchwald-Hartwig or Ullmann-type amination of halobiaryls, [3] oxidative CÀHa mination of aminobiaryls, [4] or nitrene insertion from azidobiphenyls. [5] Despite the high efficiencya nd reasonably wide scope,r esidual transition-metal impurities could adversely affect the biological properties or device performance of the final products.Tr ansition-metal-free synthesis of carbazoles has therefore undergone ar enaissance for the last few years (Scheme 1). Liu and Knochel disclosed that halogen-magnesium exchange of 2-iodo-2'-triazenobiaryls resulted in formation of carbazoles. [6] Theg roups of Chang and Antonchick reported intramolecular oxidative C À Ha mination of amino-biaryls with hypervalent iodine reagents. [7] Studer and coworkers invented an interesting approach, that is,reactions of arynes with nitrosoarenes, [8] but the yields were moderate and the regioselectivity was not as well controlled as is typically observed in aryne chemistry.T okuyama and co-workers developed ab ase-mediated cyclization of 2-amino-2'-bromobiphenyls via arynes. [9] From similar precursors,photoinduced cyclization occurs by ar adical process to yield carbazoles. [10] Kürti and co-workers disclosed facile reductive cyclization of 2-nitrobiaryls by means of PhMgBr. [11] Regardless of these elegant protocols,t here still remains ample room to develop novel strategies to prepare carbazoles without recourse to transition-metal catalysts.Recently,o ur group has been interested in developing "aromatic metamorphosis", which represents at ransformation of an aromatic system into adifferent one through partial disassembly of the starting aromatic ring. [12][13][14] Along these lines,h erein we report transition-metal-free S N Ar-based aromatic metamorphosis of dibenzothiophenes to carbazoles via dibenzothiophene dioxides.Our strategy begins with smooth oxidation of dibenzothiophenes with aqueous hydro...

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“…[21] By comparing the HOMO levels (E HOMO ) of several related molecules, it is clear that diindolo[2,3-b:2',3'-f]pyrroloA C H T U N G T R E N N U N G [3,2-b]pyrroles (such as 54) possess the highest lying HOMOs ( Table 2). [65] OFETs have been prepared from some of above-described molecular architectures and reveal promising charge-transfer mobilities. [65] OFETs have been prepared from some of above-described molecular architectures and reveal promising charge-transfer mobilities.…”

Section: Physicochemical Propertiesmentioning

confidence: 99%

1,4‐Dihydropyrrolo[3,2‐b]pyrrole and Its π‐Expanded Analogues

Janiga

Gryko

2014

Chemistry An Asian Journal

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Various approaches to the synthesis of 1,4-dihydropyrrolo[3,2-b]pyrroles are summarized. Many two- and three-step reaction sequences have been developed, and have allowed access to a broad variety of structures, including not only the parent 1,4-dihydropyrrolo[3,2-b]pyrroles, but also their π-expanded analogues. The newest approaches are critically compared with older strategies. The reactivity of these compounds is also reviewed, with special emphasis on electrophilic aromatic substitution. The synthesis of indolo[3,2-b]indole derivatives has been the subject of intense investigation. Overall, a few interesting and ingenious approaches toward these ladder-type heteroacenes have been proposed, reaching total yields in the region of 30%. Finally, the optical, electrochemical, and other physicochemical properties are presented in the broader perspective of heteropentalenes. The parent 1,4-dihydro-pyrrolo[3,2-b]pyrroles constitute the most electron-rich, simple, aromatic heterocycles, and their simple derivatives and π-expanded analogues possess strong violet, blue, or green fluorescence both in solution and in the solid state.

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A Sm(II)-Mediated Cascade Approach to Dibenzoindolo[3,2-b]carbazoles: Synthesis and Evaluation

Cited by 40 publications

References 49 publications

Transition‐Metal‐Free Synthesis of Carbazoles and Indoles by an S_NAr‐Based “Aromatic Metamorphosis” of Thiaarenes

Transition‐Metal‐Free Synthesis of Carbazoles and Indoles by an S_NAr‐Based “Aromatic Metamorphosis” of Thiaarenes

Transition‐Metal‐Free Synthesis of Carbazoles and Indoles by an S_NAr‐Based “Aromatic Metamorphosis” of Thiaarenes

1,4‐Dihydropyrrolo[3,2‐b]pyrrole and Its π‐Expanded Analogues

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A Sm(II)-Mediated Cascade Approach to Dibenzoindolo[3,2-b]carbazoles: Synthesis and Evaluation

Cited by 40 publications

References 49 publications

Transition‐Metal‐Free Synthesis of Carbazoles and Indoles by an SNAr‐Based “Aromatic Metamorphosis” of Thiaarenes

Transition‐Metal‐Free Synthesis of Carbazoles and Indoles by an SNAr‐Based “Aromatic Metamorphosis” of Thiaarenes

Transition‐Metal‐Free Synthesis of Carbazoles and Indoles by an SNAr‐Based “Aromatic Metamorphosis” of Thiaarenes

1,4‐Dihydropyrrolo[3,2‐b]pyrrole and Its π‐Expanded Analogues

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Transition‐Metal‐Free Synthesis of Carbazoles and Indoles by an S_NAr‐Based “Aromatic Metamorphosis” of Thiaarenes

Transition‐Metal‐Free Synthesis of Carbazoles and Indoles by an S_NAr‐Based “Aromatic Metamorphosis” of Thiaarenes

Transition‐Metal‐Free Synthesis of Carbazoles and Indoles by an S_NAr‐Based “Aromatic Metamorphosis” of Thiaarenes