First Perphenylated <i>carbo</i>‐Oligoacetylenes: An Extension of the Polytriacetylene Family

Rives, Arnaud; Maraval, Valérie; Saffon‐Merceron, Nathalie; Chauvin, Rémi

doi:10.1002/chem.201201555

Cited by 14 publications

(25 citation statements)

References 46 publications

(14 reference statements)

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“…The hypsochromic shift of the  max value of 6 (418 nm) with respect to 9 (453 nm) is attributed to the withdrawing effect of the CF 3 groups of 6. In the dibutatrienylacetylene (DBA) series, namely the carbo-n-butadienes, it was indeed observed that electron withdrawing substituents induce a relative hypsochromic shift [10]. Nevertheless, the two products exhibit comparable molar extinction coefficients of  6 = 73400 L.mol Although the present results confirm that this target cannot be accessible by reductive elimination from a hexa(trifluoromethyl)-hexaoxy- [6]pericyclyne, alternative strategies and future efforts deserve to be envisaged [11].…”

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confidence: 78%

First example of ring carbomer of 1,4-cyclohexadiene

et al. 2015

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While a series of carbo-mers of 1,3-cyclohexadienes was reported through the use of a specifically developed synthetic strategy, no example of their 1,4-regioisomers was known. Inspired by the methodology elaborated for the preparation of the 1,3-isomers, the synthesis of the first example of carbo-mer of 1,4-cyclohexadiene is presented. Comparison of physico-chemical properties of this first representative with those of the recently described 1,4-regioisomer, especially UV-vis absorption properties, is also addressed.

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confidence: 78%

First example of ring carbomer of 1,4-cyclohexadiene

et al. 2015

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“…In addition to optoelectronic characterization of the aryl cumulenes, they also conducted X‐ray diffraction analysis of the longest known cumulene 52 c . Other notable recent syntheses of cumulene‐containing molecules include the cumulene rotaxane 54 and the [3]cumulene 55 ,…”

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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“…The double additions of 1 were found to proceed in higher yields with aldehydes than with the propargylic phenylketone 5 that was previously reported to give perphenylated pentaynediol 3 f in 51 % yield. [4] From stereoisomeric mixtures of triyne 1, the triynediols 4 a-e were obtained as mixtures of diastereoisomers.…”

Section: Synthesis Of Pentaynediol Dba Precursors Directly From Triynmentioning

confidence: 99%

“…[1c] Such carbo-oligoacetylenes, identified generically as "1,4-PTAs", that is, 1,4-isomers of the reference polytriacetylenes (1,2-PTAs), [3] were exemplified in the perphenylated series by the DAB monomer, the di(alkynylbutatrienyl)acetylene (DaBA or DBA) dimer, and the less stable di(alkynylbutatrienylethynyl)bu-tatriene (DaBEB) trimer, capped with tri(isopropyl)silyl (TIPS) stabilizing groups (Figure 1, top). [4] In the functional series, DBAs decorated with terminal p-aminophenyl substituents (Figure 1, bottom) were also recently described in comparison with their carbo-benzene counterparts. [5a] These preliminary results showed that regarding UV/Vis absorption and redox properties, the DBA (or carbo-butadiene) backbone is much more sensitive to substituent effects than the p-carbo-benzene core.…”

Section: Introductionmentioning

confidence: 98%

“…[5b] With consideration of the photophysical and liquid crystals properties of the parent 1,4-diaryl-substituted butadienes, [6] a systematic investigation of the substitution Figure 1. Perphenylated carbo-oligoacetylenes exemplified for n = 0-3 (1,4-PTAs; E: SiiPr 3 ) relative to the reference polytriacetylene (1,2-PTA) isomers (top), [3,4] and functional n = 2 derivatives exemplified for R 1 and R 2 being 4-X-C 6 H 4 (X: NH 2 , NMe 2 , indol-N-yl, or carbazol-N-yl; bottom). [5] effect at the 1-and 10-positions of the expanded carbo-butadiene backbone was undertaken.…”

Section: Introductionmentioning

confidence: 99%

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Functional carbo‐Butadienes: Nonaromatic Conjugation Effects through a 14‐Carbon, 24‐π‐Electron Backbone

Rives¹,

Maraval²,

Saffon‐Merceron³

et al. 2013

Chemistry A European J

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A systematic study of carbo-butadiene motifs not embedded in an aromatic carbo-benzene ring is described. Dibutatrienylacetylene (DBA) targets R(1) C(R)CCC(Ph)C≡CC(Ph)CCC(R)R(2) are devised, in which R is C≡CSiiPr3 and R(1) and R(2) are R, H, or 4-X-C6 H4 , with the latter including three known representatives (X: H, NMe2 , or NH2 ). The synthesis method is based on the SnCl2 -mediated reduction of pentaynediols prepared by early or late divergent strategies; the latter allows access to a OMe-NO2 push-pull diaryl-DBA. If R(1) and R(2) are H, an over-reduced dialkynylbutatriene (DAB) with two allenyl caps was isolated instead of the unsubstituted DBA. If R(1) =R(2) =R, the tetraalkynyl-DBA target was obtained, along with an over-reduced DBA product with a 12-membered 1,2-alkylidene-1H2 ,2H2 -carbo-cyclobutadiene ring. X-ray crystallography shows that all of the acyclic DBAs adopt a planar trans-transoid-trans configuration. The maximum UV/Vis absorption wavelength is found to vary consistently with the overall π-conjugation extent and, more intriguingly, with the π-donor character of the aryl X substituents, which varies consistently with the first (reversible) reduction potential and first (irreversible) oxidation peak, as determined by voltammetry.

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First Perphenylated carbo‐Oligoacetylenes: An Extension of the Polytriacetylene Family

Cited by 14 publications

References 46 publications

First example of ring carbomer of 1,4-cyclohexadiene

First example of ring carbomer of 1,4-cyclohexadiene

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

Functional carbo‐Butadienes: Nonaromatic Conjugation Effects through a 14‐Carbon, 24‐π‐Electron Backbone

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