Reduction of Ethynylenes to Vinylenes in a Macrocyclic π-Extended Thiophene Skeleton Under McMurry Coupling Conditions

Shirahata, Keigo; Takashika, Masataka; Hirabayashi, Kazunori; Hasegawa, Masashi; Otani, Hiroyuki; Yamamoto, Keitaro; Ie, Yutaka; Shimizu, Toshio; Aoyagi, Shinobu; Iyoda, Masahiko

doi:10.1021/acs.joc.0c02080

Cited by 10 publications

(8 citation statements)

References 50 publications

(38 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…However, twofold oxidation of the macrocycle with the n-butyl chains indicated that the compound does feature Type I-CA. An expanded analogue of the macrocycle with the thienylene subunits in Figure 7a was also shown to crystallize in dimers (CCDC number: 1996534), 78 whereas a contracted analogue of the macrocycle with furanylene subunits in Figure 6a exhibited chain-like packing (CCDC number: 1166262) as well as Type I-CA. 79 Other structurally related macrocycles that may feature Type III-CA can also be found in the literature, such as [24]annulene tetroxide in all-cis configuration and its thiophene analog.…”

Section: Concealed Antiaromaticity Revealable In Intermolecular Inter...mentioning

confidence: 99%

Concealed antiaromaticity

Glöcklhofer

2023

Preprint

View full text Add to dashboard Cite

Numerous articles in the recent literature report molecules that are claimed to be antiaromatic, as they feature a formal 4n π-electron system. The purported antiaromaticity often serves well as an explanation for some of the observed properties, but it neglects the actual local aromaticity of the molecules, which often feature multiple subunits with 4n+2 π-electrons besides the formal 4n π-electron system. This has led to considerable criticism from those who believe that the term antiaromatic should not be used for any molecule with a formal 4n π-electron system but should be reserved for truly antiaromatic molecules. To reconcile the different viewpoints, the term and concept of concealed antiaromaticity is introduced here. The concept accepts that many of the molecules claimed to be antiaromatic are not truly antiaromatic. However, it acknowledges that this does not prevent those molecules from exhibiting behaviour under certain conditions that would normally be expected for antiaromatic molecules, due to the formal, concealed 4n π-electron system that characterizes these molecules. Based on the conditions under which the molecules can behave like antiaromatic molecules, three types of concealed antiaromaticity are distinguished here: concealed antiaromaticity revealable in redox reactions (Type I-CA), upon excitation (Type II-CA), and in intermolecular interactions (Type III-CA). The concept of concealed antiaromaticity will enable the conscious, rational design of molecules that show the desirable properties of antiaromatic molecules while avoiding or diminishing the undesirable properties, namely the low stability of truly antiaromatic molecules. This will yield molecules and materials with highly interesting properties for a broad range of applications, from organic electronics to supramolecular chemistry.

show abstract

Section: Concealed Antiaromaticity Revealable In Intermolecular Inter...mentioning

confidence: 99%

Concealed antiaromaticity

Glöcklhofer

2023

Preprint

View full text Add to dashboard Cite

show abstract

“…Another application of the McMurry reaction is related to the reduction of ethynylene-linkage substrates to form a photosensitive product with vinylene-linkage units, 152 and 153. 88 Oligothiophenes with π-conjugated macrocycles exhibit optoelectronic properties for multifunctional materials. Based on Shirahata's experiment, the yield of oligothiophene depends on the reaction temperature, the amount of titanium, and the thiophene substituent.…”

Section: Applications Of the Mcmurry Reactionmentioning

confidence: 99%

“…Based on Shirahata's experiment, the yield of oligothiophene depends on the reaction temperature, the amount of titanium, and the thiophene substituent. 88 …”

Section: Applications Of the Mcmurry Reactionmentioning

confidence: 99%

“…Based on Shirahata's experiment, the yield of oligothiophene depends on the reaction temperature, the amount of titanium, and the thiophene substituent. 88 new novel synthetic of oligomers is a combination of the McMurry reaction, the Wittig reaction, and the Heck reaction applied to synthesize vinylene-linked molecules, 155, specically phenothiazinevinylene-based oligomers. 89 Phenothiazine has a bent-shape conformation, known as "buttery" geometry, that can induce molecular aggregation and excimer formation.…”

Section: Synthesis Of Non-natural Productsmentioning

confidence: 99%

See 1 more Smart Citation

Recent advances of carbonyl olefination via McMurry coupling reaction

2022

View full text Add to dashboard Cite

show abstract

“…In this work, we report a facile, gentle and low-cost synthetic route to prepare AEMs with both ether-free architecture for endowing alkaline stability, and phase-separated morphol-ogy to enhance the OH À conductivity. For the first time, we employed the single-step McMurray coupling polymerization [21,22] to synthesize π-conjugated AEMs under mild conditions, and avoid hazardous reagents or noble metal catalysts. The π-conjugated system in AEM is composed of a benzene ring and a double bond.…”

Section: Introductionmentioning

confidence: 99%

A π‐Conjugated Anion‐Exchange Membrane with an Ordered Ion‐Conducting Channel via the McMurray Coupling Reaction

Zhang

Sun

et al. 2022

Angewandte Chemie

View full text Add to dashboard Cite

The McMurry coupling is a facile, gentle and low‐cost chemical reaction for synthesizing. Here, for the first time, we employed the McMurry coupling reaction to prepare π‐conjugated anion exchange membranes (AEMs). The inter‐chain π‐π stacking between adjacent benzene rings induces directional self‐assembly aggregation and enables highly ordered ion‐conductive channels. The resulting structure was characterized through UV/VIS spectrum, X‐ray diffraction (XRD) pattern, small‐angle X‐ray scattering (SAXS), transmission electron microscopy (TEM) and density functional theory (DFT) calculations, leading to high OH− conductivity of 135.5 mS cm−1 at 80 °C. Furthermore, the double bonds in the π‐conjugated system also trigger in situ self‐crosslinking of the AEMs to enhance dimensional and alkaline stability. Benefiting from this advantage, the as‐obtained Cr‐QPPV‐2.51 AEM exhibits superior alkaline stability (95 % conductivity retention after 3000 hrs in 1 M KOH at 80 °C) and high mechanical strength of 34.8 MPa. Moreover, the fuel cell using Cr‐QPPV‐2.51 shows a maximum peak power density of 1.27 W cm−2 at 80 °C.

show abstract

Reduction of Ethynylenes to Vinylenes in a Macrocyclic π-Extended Thiophene Skeleton Under McMurry Coupling Conditions

Cited by 10 publications

References 50 publications

Concealed antiaromaticity

Concealed antiaromaticity

Recent advances of carbonyl olefination via McMurry coupling reaction

A π‐Conjugated Anion‐Exchange Membrane with an Ordered Ion‐Conducting Channel via the McMurray Coupling Reaction

Contact Info

Product

Resources

About