Cyclic [5]Paraphenyleneacetylene: Synthesis, Properties, and Formation of a Ring‐in‐Ring Complex Showing a Considerably Large Association Constant and Entropy Effect

Kawase, Takeshi; Nishiyama, Yoshitaka; Nakamura, Tomiyo; Ebi, Takahiro; Matsumoto, Kouzou; Kurata, Hiroyuki; Oda, Masaji

doi:10.1002/anie.200603707

Cited by 65 publications

(56 citation statements)

References 66 publications

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“…An early example of “Russian doll” or “onion‐type” complexes was reported by Kawase, Oda et al. in 2004 (Figure b) . The authors found that [6]CPPA fits into the cavity of [9]CPPA and they determined a binding constant of 1180±140 m −1 (0 °C) for two π‐extended analogues ( 4 and 5 ; Figure b) that are more soluble than the parent compounds.…”

Section: Host–guest Chemistrymentioning

confidence: 99%

The Supramolecular Chemistry of Strained Carbon Nanohoops

2019

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Since 1996, a growing number of strained macrocycles, comprising only sp2‐ or sp‐hybridized carbon atoms within the ring, have become synthetically accessible, with the [n]cycloparaphenyleneacetylenes (CPPAs) and the [n]cycloparaphenylenes (CPPs) being the most prominent examples. Now that robust and relatively general synthetic routes toward a diverse range of nanohoop structures have become available, the research focus is beginning to shift towards the exploration of their properties and applications. From a supramolecular chemistry perspective, these macrocycles offer unique opportunities as a result of their near‐perfect circular shape, the unusually high degree of shape‐persistence, and the presence of both convex and concave π‐faces. In this Minireview, we give an overview on the use of strained carbon‐rich nanohoops in host–guest chemistry, the preparation of mechanically interlocked architectures, and crystal engineering.

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Section: Host–guest Chemistrymentioning

confidence: 99%

The Supramolecular Chemistry of Strained Carbon Nanohoops

2019

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“…[12] X-ray crystallographic and spectroscopic data showed that the alkyne unit of even the smallest macrocycle 1 is less bent than that of dibenzo-fused cyclooctyne.I ns tark contrast to this finding,however, macrocycle 1 undergoes rapid [2+ +2]CA-RC with TCNE at temperatures as low as 0 8 8Ci nt he absence of any catalyst, whereas cyclooctyne derivatives often require heating to react. [24][25][26] Previously reported syntheses of cycloparaphenyleneacetylenes (CPPAs) were based on 1) the brominationdehydrobromination of macrocyclic alkene precursors obtained by McMurry coupling [27][28][29][30] or 2) alkyne metathesis followed by reductive aromatization, [31] which provided access to al imited number of highly symmetric derivatives with multiple alkyne units.While the backbone-incorporated alkynes have recently been shown to undergo triple SPAAC reaction, single alkynes could not be addressed selectively owing to the increasing reactivity with each CA step. [24][25][26] Previously reported syntheses of cycloparaphenyleneacetylenes (CPPAs) were based on 1) the brominationdehydrobromination of macrocyclic alkene precursors obtained by McMurry coupling [27][28][29][30] or 2) alkyne metathesis followed by reductive aromatization, [31] which provided access to al imited number of highly symmetric derivatives with multiple alkyne units.While the backbone-incorporated alkynes have recently been shown to undergo triple SPAAC reaction, single alkynes could not be addressed selectively owing to the increasing reactivity with each CA step.…”

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confidence: 99%

Strain‐Promoted Reactivity of Alkyne‐Containing Cycloparaphenylenes

et al. 2018

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An ew class of macrocyclic angle-strained alkynes whose size and reactivity can be precisely tuned by modular organic synthesis is disclosed. Detailed analysis of the sizedependent structural and electronic properties provides evidence for considerable distortion of the alkyne units incorporated into the cycloparaphenylene (CPP)-derived macrocycles. The remarkable increase of the alkyne reactivity with decreasing macrocycle size in [2+ +2]cycloaddition-retrocyclization was investigated by joint experimental and theoretical studies and the thermodynamic and kinetic parameters that govern this reaction were unraveled. Additionally,e ven the largest, least strained macrocycle in this series was found to undergo strainpromoted azide-alkyne cycloaddition (SPAAC) efficiently under mild conditions,t herebyp aving the way to the application of alkyne-containing CPPs as fluorescent "clickable" macrocyclic architectures.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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“…This finding then improved the access to [6]CPPA as well. The modified McMurry coupling afforded cyclopentamer 39 , which could be smoothly converted to [5]CPPA 33 b as the smallest CPPA so far reported (Figure b) . The coupling of dialdehydes 38 and 40 (1:1 ratio) enabled production of the precursor of [7]CPPA 33 d (Figure c) .…”

Section: Angle‐strained Alkyne‐containing π‐Conjugated Macrocyclesmentioning

confidence: 99%

π‐Conjugated Macrocycles Bearing Angle‐Strained Alkynes

Miki

Ohe

2019

Chemistry A European J

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Angle‐strained alkyne‐containing π‐conjugated macrocycles are attractive compounds both in functional materials chemistry and biochemistry. Their interesting reactivity as well as photophysical and supramolecular properties have been revealed in the past three decades. This review highlights the recent advances in angle‐strained alkyne‐containing π‐conjugated macrocycles, especially their synthetic methods, the bond angles of alkynes (∠sp at C≡C−C), and their functions. The theoretical and experimental research on cyclo[n]carbons and para‐cyclophynes consisting of ethynylenes and para‐phenylenes are mainly summarized. Related macrocycles bearing other linkers, such as ortho‐phenylenes, meta‐phenylenes, heteroaromatics, biphenyls, extended aromatics, are also overviewed. Bond angles of strained alkynes in π‐conjugated macrocycles, which are generable, detectable, and isolable, are summarized at the end of this review.

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Cyclic [5]Paraphenyleneacetylene: Synthesis, Properties, and Formation of a Ring‐in‐Ring Complex Showing a Considerably Large Association Constant and Entropy Effect

Cited by 65 publications

References 66 publications

The Supramolecular Chemistry of Strained Carbon Nanohoops

The Supramolecular Chemistry of Strained Carbon Nanohoops

Strain‐Promoted Reactivity of Alkyne‐Containing Cycloparaphenylenes

π‐Conjugated Macrocycles Bearing Angle‐Strained Alkynes

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