Convenient Synthesis of Tetra- and Hexaarylanthracenes by Means of RuH2(CO)(PPh3)3-Catalyzed C−H Arylation of Anthraquinone with Arylboronates

Kitazawa, Kentaroh; Kochi, Takuya; Sato, Mitsuo; Kakiuchi, Fumitoshi

doi:10.1021/ol900393x

Cited by 64 publications

(27 citation statements)

References 40 publications

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“…Rio and co‐workers first demonstrated this method in 1948 with the reduction of an 9,10‐anthracene diol to the desired substituted 9,10‐bis(phenylethynyl)anthracene in nearly quantitative yield (see Scheme c) . In 2009, Kakiuchi and co‐workers were able to reduce anthraquinone 94 to tetraarylanthracene 95 by stirring the dione in aqueous acetic acid with HI for four days at 140 °C (Scheme ) …”

Section: Deoxygenation Of 14‐diols Using I− Sourcesmentioning

confidence: 99%

“…[13,18,130,134] In 2009, Kakiuchi and co-workers were able to reduce anthraquinone 94 to tetraarylanthracene 95 by stirring the dione in aqueous acetic acid with HI for four days at 140 8C(Scheme 39). [135] Only af ew further examples for the HI-mediated reductive aromatization have been reported. Chamberlin and co-workers [136] andB endikov and co-workers [137] synthesized as eries of optoelectronically interesting rubrene analogues, while the higherh omologues 96 a,b [138] were synthesized and studied by Kafafi and co-workers( Scheme 40).…”

Section: Hi-mediated Reductionmentioning

confidence: 99%

“…ChemPlusChem 2017, 82,967 -1001 www.chempluschem.org and 100, [145] as well as anthracenes 101 [135] and 102 [146] -the latter used as ap recursor for ab lue OLED emitter.A lso of interest are two-dimensional acenes, such as bisanthene 103 [147] and laterally extended bisanthenes, ac lass of compounds that exhibit small band gaps andnear-IR absorption (Figure 9). [148] There are relativelyf ew reports of this reduction method, probablyd ue to moderate yields and by-product formation found in most of the reported examples.…”

Section: Ki/nai Nah 2 Po 2 -Mediated Reduction With Acohmentioning

confidence: 99%

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Reductive Aromatization/Dearomatization and Elimination Reactions to Access Conjugated Polycyclic Hydrocarbons, Heteroacenes, and Cumulenes

et al. 2017

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Acenes, heteroacenes, conjugated polycyclic hydrocarbons, and polycyclic aromatic hydrocarbons (collectively referred to in this review as conjugated polycyclic molecules, CPMs) have fascinated chemists since they were first isolated and synthesized in the mid 19th century. Most recently, these compounds have shown significant promise as the active components in organic devices (e.g., solar cells, thin‐film transistors, light‐emitting diodes, etc.), and, since 2001, a plethora of publications detail synthetic strategies to produce CPMs. In this review, we discuss reductive aromatization, reductive dearomatization, and elimination/extrusion reactions used to form CPMs. After a brief discussion on early methods to synthesize CPMs, we detail the use of reagents used for the reductive (de)aromatization of precursors containing 1,4‐diols/diethers, including SnCl2 and iodide (I−). Extension of these methods to carbomers and cumulenes is briefly discussed. We then describe low‐valent metal species used to reduce endoxides to CPMs, and discuss the methods to directly reduce acenediones and acenones to the respective acene. In the final section, we describe methods used to affect aromatization to the desired CPM via extrusion of small, volatile molecules.

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Section: Deoxygenation Of 14‐diols Using I− Sourcesmentioning

confidence: 99%

Section: Hi-mediated Reductionmentioning

confidence: 99%

Section: Ki/nai Nah 2 Po 2 -Mediated Reduction With Acohmentioning

confidence: 99%

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Reductive Aromatization/Dearomatization and Elimination Reactions to Access Conjugated Polycyclic Hydrocarbons, Heteroacenes, and Cumulenes

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“…To develop the properties of anthracene derivatives further, the synthesis of tetraarylanthracene derivatives at various positions is considered to be an important area with significant potential. The syntheses of 2,6,9,10-tetraarylanthracene derivatives 2b,3 and 1,4,5,8-tetraarylanthracenes 4 have been achieved. However, to our knowledge, the synthesis of 1,3,5,7-tetraarylanthracenes is without precedent.…”

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confidence: 99%

Fourfold C–H Borylation of Anthracene: 1,3,5,7-Tetraborylanthracene and Its Application to 1,3,5,7-Tetraarylanthracenes

2017

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Iridium-catalyzed direct tetraborylation of anthracene to give 1,3,5,7-tetrakis(Bpin)anthracene 5 was achieved by using a combination of [Ir(OMe)(COD)] 2 and tmphen as the catalyst.Compound 5 was applied to the synthesis of 1,3,5,7-tetraarylanthracenes 7 as a new molecular entity. The latter showed long fluorescence lifetime in the solid state. Keywords: C-H borylation | Anthracene | Cross-couplingAnthracene derivatives as π-electronic cores are useful building blocks for materials used in optoelectronics 1 and for organic semiconductors.2 To date, most studies on anthracene derivatives have focused on 9,10-or 2,6-diarylanthracene derivatives and 9,10-or 2,6-bis(arylethynyl)anthracene derivatives. To develop the properties of anthracene derivatives further, the synthesis of tetraarylanthracene derivatives at various positions is considered to be an important area with significant potential. The syntheses of 2,6,9,10-tetraarylanthracene derivatives 2b,3 and 1,4,5,8-tetraarylanthracenes 4 have been achieved. However, to our knowledge, the synthesis of 1,3,5,7-tetraarylanthracenes is without precedent.Iridium-catalyzed direct CH borylation of aromatic compounds using bis(pinacolato)diboron (B 2 pin 2 ) is a very useful reaction for the synthesis of arylboronic acid pinacol esters, 5 which are reagents for the SuzukiMiyaura cross-coupling reaction.6 Under typical reaction conditions involving a combination of [Ir(OMe)(COD)] 2 and 4,4¤-di-tert-butyl-2,2¤-bipyridine (dtbpy) as the catalyst, direct CH borylation of aromatic compounds proceeds with sterically driven regioselectivity; this usually means that the position ortho to the substituent on the same ring and the peri-position on the adjacent ring do not react (ortho/peri-prohibition).5 This is also the case for linear acenes.7 Thus, Ir-catalyzed direct diborylation of anthracene under the typical reaction conditions selectively produces a 1:1 mixture of 2,6-and 2,7-bis(Bpin)anthracenes 1 and 2 (Chart 1).7c Recently, Scott and Marder developed multiborylation of polyaromatic hydrocarbons such as pyrene and corannulene at the peri-positions by using a combination of [Ir(OMe)(COD)] 2 and 4,4¤-dimethyl-2,2¤-bipyridine (dmbpy) as catalyst with a catalytic amount of t-BuOK.8 It is known that 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen) is an electronrich ligand that can enhance the activity of the resulting Ircatalyst. 9 Here, we report the Ir-catalyzed direct tetraborylation of anthracene to give 1,3,5,7-tetrakis(Bpin)anthracene 5 (Chart 1) by using a combination of [Ir(OMe)(COD)] 2 and tmphen as a catalyst. We also describe the application of 5 to the synthesis of 1,3,5,7-tetraarylanthracenes 7 as a new molecular entity; the latter showed long fluorescence lifetime in the solid state. 10The reaction of anthracene (0.1 M) and B 2 pin 2 (5 equiv) in the presence of [Ir(OMe)(COD)] 2 (20 mol %) and tmphen (40 mol %) in cyclohexane at 80°C for 48 h gave a mixture of 1,3,5,7-tetrakis(Bpin)anthracene 5, 1,3,7-tris(Bpin)anthracene 3, and 1,3,6-tris(Bpin)anthracene 4 in ...

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“…Interestingly,i th as been applied to the syntheses of several sterically congested anthracenes. [16][17][18][19] Intrigued,w ea dded phenyllithium to ar efluxing suspension of octaphenylanthraquinone [20] (4)i nd ry benzene. The diol intermediate, whichw as isolated from the reaction mixture but not purified, was treatedw ith SnCl 2 and HCl in refluxingT HF to form 1 in 52 %y ield, a5 0-foldi mprovement over its original synthesis (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

A Superior Synthesis of Longitudinally Twisted Acenes

Clevenger

Kumar

Menuey

et al. 2017

Chemistry A European J

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Seven longitudinally twisted acenes (an anthracene, two tetracenes,t hree pentacenes, and ah exacene) have been synthesizedb yt he addition of aryllithium reagents to the appropriate quinone precursors, followed by SnCl 2 -mediatedr eductiono ft heir diol intermediates, and severalo ft hese acenesh ave been crystallographicallyc haracterized. The new syntheses of the three previously reported twisted acenes, decaphenylanthracene (1), 9,10,11,20,21,22-hexaphenyltetrabenzo[a,c,l,n]pentacene( 2), and 9, 10,11,12,13,14,15,16-octaphenyldibenzo[a,c]tetracene (14), resulted in ar eductiono ft he number of synthetic steps.A saconsequence their overall yields werei ncreased by factors of 50-, 24-, and 66-fold, respectively.A ll of the twisted acenes yntheses reported here are suitable fort he synthesis of at least gram quantities of these remarkable hydrocarbon materials.

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Convenient Synthesis of Tetra- and Hexaarylanthracenes by Means of RuH₂(CO)(PPh₃)₃-Catalyzed C−H Arylation of Anthraquinone with Arylboronates

Cited by 64 publications

References 40 publications

Reductive Aromatization/Dearomatization and Elimination Reactions to Access Conjugated Polycyclic Hydrocarbons, Heteroacenes, and Cumulenes

Reductive Aromatization/Dearomatization and Elimination Reactions to Access Conjugated Polycyclic Hydrocarbons, Heteroacenes, and Cumulenes

Fourfold C–H Borylation of Anthracene: 1,3,5,7-Tetraborylanthracene and Its Application to 1,3,5,7-Tetraarylanthracenes

A Superior Synthesis of Longitudinally Twisted Acenes

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