Strategies for the Synthesis of Higher Acenes

Dorel, Ruth; Echavarren, Antonio M.

doi:10.1002/ejoc.201601129

Cited by 80 publications

(62 citation statements)

References 145 publications

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“…For example, pentacene is the best available organic p-type semiconductor, but larger members could be even more useful. 104 Excellent syntheses of octacene and nonacene derivatives have been carried out by Echavarren, 105–106 and Bettinger and coworkers have developed a building block method using iterative Diels Alder reactions (Figure 3b). 107 Combination of 5,6,7,8-tetramethylenebicyclo[2.2.2]oct-2-ene and an aryne dienophile generated by treatment of 1,2-dibromobenzene with n -BuLi led to formation of a cycloadduct with a terminating diene moiety.…”

Section: Many Customized Iterative Synthesis Methods Have Already Beementioning

confidence: 99%

Towards the generalized iterative synthesis of small molecules

2018

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Small molecules have extensive untapped potential to benefit society, but access to this potential is too often restricted by limitations inherent to the customized approach currently used to synthesize this class of chemical matter. In contrast, the “building block approach”, i.e., generalized iterative assembly of interchangeable parts, has now proven to be a highly efficient and flexible way to construct things ranging all the way from skyscrapers to macromolecules to artificial intelligence algorithms. The structural redundancy found in many small molecules suggests that they possess a similar capacity for generalized building block-based construction. It is also encouraging that many customized iterative synthesis methods have been developed that improve access to specific classes of small molecules. There has also been substantial recent progress toward the iterative assembly of many different types of small molecules, including complex natural products, pharmaceuticals, biological probes, and materials, using common building blocks and coupling chemistry. Collectively, these advances suggest that a generalized building block approach for small molecule synthesis may be within reach.

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Section: Many Customized Iterative Synthesis Methods Have Already Beementioning

confidence: 99%

Towards the generalized iterative synthesis of small molecules

2018

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“…The addition of a nucleophile to a dione followed by reduction of the subsequent diol with SnCl 2 (addition–reduction sequence) is one of the most widely used methods to form CPMs (Scheme ) . A simple SciFinder search of this transformation yields over 400 publications, the overwhelming majority of which were published after 2001.…”

Section: Snii‐mediated Reduction Of Diolsmentioning

confidence: 99%

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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“…To overcome the inherent fragility of long acenes and to improve their solubility and processability, it is possible to attach electron‐deficient or bulky substituents or to introduce heteroatoms into the acene framework such as sulfur or nitrogen atoms . However, the electronic properties of such materials cannot be compared with their parent acenes.…”

Section: Introductionmentioning

confidence: 99%

“…However, the electronic properties of such materials cannot be compared with their parent acenes. Since the latter are poorly soluble, prone to (photo)oxidation and dimerise in solution, their synthesis remains “a formidable challenge” to quote R. Dorel and A. M. Echavarren . The only way to study them is to prepare more stable, and if possible soluble, precursors that can be converted in a final step in the solid state through a unimolecular process into the target acenes.…”

Section: Introductionmentioning

confidence: 99%

A Practical General Method for the Preparation of Long Acenes

Jančařík

Levet

Gourdon

2019

Chemistry A European J

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The field of long acenes, the narrowest of the zig‐zag graphene nanoribbons, has been an area of significant interest in the past decade because of its potential applications in organic electronics, spintronics and plasmonics. However the low solubility and high reactivity of these compounds has so far hindered their preparation on large scales. We report here a concise strategy for the synthesis of higher acenes through Diels–Alder condensation of arynes with a protected tetraene ketone. After deprotection by cleavage of the ketal, the obtained monoketone precursors cleanly yield the corresponding acenes through quantitative cheletropic thermal decarbonylation in the solid state, at moderate temperatures of 155 to 205 °C. This approach allows the preparation of heptacene, benzo[a]hexacene, cis‐ and trans‐dibenzopentacene and offers a valuable new method for the synthesis of even larger acenes.

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Strategies for the Synthesis of Higher Acenes

Cited by 80 publications

References 145 publications

Towards the generalized iterative synthesis of small molecules

Towards the generalized iterative synthesis of small molecules

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

A Practical General Method for the Preparation of Long Acenes

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