Elimination Strategy for Aromatic Acetylenes

Orita, Akihiro; Otera, Junzo

doi:10.1021/cr050560m

Cited by 55 publications

(21 citation statements)

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“…44 This reaction produced a mixture of cyclic oligomers, which can be separated easily by gel permeation chromatography on polystyrene with toluene or chloroform as an eluent to afford 30p-10T8A (39%), 90p-15T12A (9.4%), 120p-20T16A (6.2%), 150p-25T20A (3.9%), and 180p-30T24A (2.3%), together with a 1 : 3 mixture of the E,Z-and Z,Z-isomers of 10T8A (7%) in total 65.5% yield (Scheme 11). For the synthesis of 12T12A by using 'double elimination procedure', 46 the sulfone dianion prepared from 41 was reacted with the dialdehyde 34 (1 equiv.). Variable temperature (VT) NMR spectroscopic studies revealed that 10T8A-30T24A show symmetrical D nh structures even at À60 1C, reflecting a rapid conformational change in solutions.…”

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confidence: 99%

Multifunctional π-expanded oligothiophene macrocycles

2015

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This tutorial review summarizes recent progress in the design, synthesis, and multifunctional properties of fully conjugated macrocyclic π-systems. We focus on the π-expanded oligothiophene macrocycles after a short survey of macrocyclic conjugated loops and belts such as [n]cycloparaphenylenes, cyclic[n]para-phenylacetylenes, [4]cyclo-2,8-crysenylenes, and cyclo[n]thiophenes. Fully conjugated π-expanded oligothiophene macrocycles possess shape-persistent but sometimes pliable π-frames, and the electronic and optoelectronic properties of the macrocycles largely depend on the π-systems inserted into the oligothiophene macrocycles. Among them, the π-expanded oligothiophene macrocycle composed of 2,5-thienylenes, ethynylenes, and vinylenes is one of the most widely applicable macrocycles for constructing multifunctional π-systems. These π-expanded oligothiophene macrocycles from small to very large ring sizes can be prepared via a short step procedure, and their various solid state structures can be determined by X-ray analysis. Since these macrocycles have inner and outer domains, specific information concerning structural, electronic, and optical properties is expected. Furthermore, π-expanded oligothiophene macrocycles with alkyl substituents exhibit various morphologies depending on nanophase separation of molecules, and a morphological change is observed for the molecular switch.

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Section: View Article Onlinementioning

confidence: 99%

Multifunctional π-expanded oligothiophene macrocycles

2015

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“…The elimination of substituted C=C or even C−C bonds are classical protocols employable for generating C≡C bonds, such as dehydrohalogenation of alkyl vic ‐dihalides or vinyl halides (Scheme a and 1b). New elimination reactions also have been discovered to produce sophisticate molecular structures . C≡C bonds can be also prepared from carbonyl groups, such as from aldehydes by the Corey–Fuchs reaction (Scheme c) or from aryl ketone by the Seyferth–Gilbert homologation (Scheme d), and from 1,1‐diarylvinyl halide or 1,1‐dibromo‐olefin by the Fritsch‐Buttenberg‐Wiechell rearrangement (Scheme e).…”

Section: Introductionmentioning

confidence: 99%

Quantitative Construction of C≡C Bond: Renaissance of Reductive Coupling of Benzotribromides Promoted by Cu/Polyamine

Ren

Wang

2018

ChemistrySelect

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“…Cyclo[ n ](3,4‐dibutyl‐2,5‐thienyleneethynylene)s 140 a – 140 c were synthesized through bromination of macrocycles 139 c – 139 e followed by dehydrobromination (Figure a) . Iyoda and co‐workers developed two alternative synthetic routes to cyclo[ n ](3,4‐dibutyl‐2,5‐thienyleneethynylene)s, such as 1) the intramolecular Sonogashira–Hagihara coupling (Figure b) and 2) the double‐elimination reaction developed by Orita and Otera (Figure c). The intramolecular Sonogashira–Hagihara coupling of linear oligomers 141 a and 141 b afforded cyclooctamer 140 b and cyclodecamer 140 c , respectively.…”

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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Elimination Strategy for Aromatic Acetylenes

Cited by 55 publications

References 218 publications

Multifunctional π-expanded oligothiophene macrocycles

Multifunctional π-expanded oligothiophene macrocycles

Quantitative Construction of C≡C Bond: Renaissance of Reductive Coupling of Benzotribromides Promoted by Cu/Polyamine

π‐Conjugated Macrocycles Bearing Angle‐Strained Alkynes

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