Conjugated Macrocycles: Concepts and Applications

Iyoda, Masahiko; Yamakawa, Jun; Rahman, Mohammad A.

doi:10.1002/anie.201006198

Cited by 499 publications

(316 citation statements)

References 365 publications

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“…The reaction of 7 ]·6dmso·1.32H 2 O (237b) was formed upon the recrystallization of 237a product from dimethyl sulfoxide. As a result of the double-bond character of the central N-C linkage, the thiol tautomer could exist as thiol form A and thiol form B, and adopted a syn or anti configuration.…”

Section: +mentioning

confidence: 99%

Neutral discrete metal–organic cyclic architectures: Opportunities for structural features and properties in confined spaces

Thanasekaran

Lee

2014

Coordination Chemistry Reviews

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Section: +mentioning

confidence: 99%

Neutral discrete metal–organic cyclic architectures: Opportunities for structural features and properties in confined spaces

Thanasekaran

Lee

2014

Coordination Chemistry Reviews

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“…[3] Apart from their medicinal applications, their applications range from "shape-persistent macrocycles" [4] to synthetic receptors, [5] sensors, and porous materials. [6] Therefore, methods to prepare new macrocyclic structures are of interest, especially if the synthetic procedures fulfill two requisites: the methods employed should be simple and it should be possible to tailor the final structure.…”

Section: Introductionmentioning

confidence: 99%

The Reversible Nicholas Reaction in the Synthesis of Highly Symmetric Natural‐Product‐Based Macrocycles

et al. 2014

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Two different approaches to highly symmetric macrocycles by reversible Nicholas reactions have been developed. The first sequence uses a bis[Co2(CO)6] complex derived from a double propargylic alcohol supporting two natural product moieties. The reactions with BF3·OEt2 and different benzene dimethanols yielded either (1:1) or (2:2) adducts, depending essentially on the nature of the tether joining both Co clusters. Alternatively, the Nicholas reactions of Co‐complexed propargyl alcohol templates with one steroid and one monoterpene fragment as well as one aromatic terminus containing an alcohol moiety yielded the corresponding macrocycles derived from self‐dimerization. Both routes to macrocycles are complementary and efficiently produce sophisticated natural‐product‐containing structures.

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“…[1][2][3][4][5][6][7][8] Since the first syntheses of [9]CPP, [12]CPP, and [18]CPP by Bertozzi and co-workers in 2008, 9 significant progress toward the synthesis of CPPs and CPP analogues of various sizes has been made by Jasti, [9][10][11][12][13][14][15][16] Itami, [17][18][19][20][21][22][23][24][25][26][27][28] Yamago, [29][30][31][32][33][34][35] and their respective co-workers, as well as by other research groups. [36][37][38][39][40][41][42][43] Consequently, several unique properties of CPPs, such as their size-dependent photophysical [44][45]…”

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confidence: 99%

Selective and Gram-Scale Synthesis of [6]Cycloparaphenylene

Kayahara

Patel

Xia

et al. 2015

Synlett

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A selective, practical, and large-scale synthesis of [6]cycloparaphenylene, the second smallest cycloparaphenylene to be synthesized, was achieved in nine steps starting from commercially available 1,4-dibromobenzene and 4′-bromobiphenyl-4-ol. The key intermediate, cis-1,4-(4-bromophenyl)-1,4-bis(triethylsiloxy)cyclohexa-2,5-diene, was prepared on a large scale (>20 g) and was selectively dimerized to form a cyclic precursor of [6]cycloparaphenylene by platinum-mediated assembly and subsequent reductive elimination. Deprotection of the triethylsilyl group and subsequent tetrachlorostannic acid (H 2 SnCl 4 )-mediated reductive aromatization gave [6]cycloparaphenylene in 23% overall yield from the commercially available substrates on gram scale.Cycloparaphenylenes (CPPs; Figure 1) have garnered significant interest because of their unique structures, which resemble the basic structural units of the sidewalls of carbon nanotubes, and for their vast potential for applications in materials science and technology. 1-8 Since the first syntheses of [9]CPP, [12]CPP, and [18]CPP by Bertozzi and co-workers in 2008, 9 significant progress toward the synthesis of CPPs and CPP analogues of various sizes has been made by Jasti, [9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35] and their respective co-workers, as well as by other research groups. [36][37][38][39][40][41][42][43] Consequently, several unique properties of CPPs, such as their size-dependent photophysical 44-50 and redox properties 31,51-55 and their size-complementary host-guest chemistries, 56-59 have been revealed.The synthesis of small CPPs has recently attracted significant attention because smaller CPPs possess narrower HOMO-LUMO energy gaps than do larger CPPs, 31 which is advantageous in relation to applications in organic electronic materials. For example, [5]CPP, the smallest CPP synthesized to date, possesses the narrowest HOMO-LUMO gap among known CPPs and it has a similar energy gap to that of buckminsterfullerene. 14,34 In addition, [5]CPP can be prepared on a large scale. 60 [6]CPP, the second smallest CPP, which shows a unique crystal packing in the solid state, has been prepared by Xia and Jasti 13 and by Yamago and co-workers (Scheme 1); 33 however, the reported methods were inefficient for largescale preparation of the compound. Specifically, in Jasti's synthesis, the cyclic precursor 1, which bears two cis-1,4-dimethoxycyclohexa-2,5-diene-1,4-diyl units, was treated with a 1,4-diborylbenzene derivative to give the cyclic intermediate 2; this was reductively aromatized with sodium naphthalenide at -78 °C to give [6]CPP [Scheme 1 (a)]. However, the low coupling efficiency of 1 to form 2, the low overall yield (0.7%), and the harsh reaction conditions required to form [6]CPP from 2 limit the potential for largescale production. In Yamago's synthesis, the bisplatinum complex 3 was homocoupled by a nickel(0)-mediated Yamamoto coupling 61,62 to form the cyclic tetraplatinum complex 4; subsequen...

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Conjugated Macrocycles: Concepts and Applications

Cited by 499 publications

References 365 publications

Neutral discrete metal–organic cyclic architectures: Opportunities for structural features and properties in confined spaces

Neutral discrete metal–organic cyclic architectures: Opportunities for structural features and properties in confined spaces

The Reversible Nicholas Reaction in the Synthesis of Highly Symmetric Natural‐Product‐Based Macrocycles

Selective and Gram-Scale Synthesis of [6]Cycloparaphenylene

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