Synthesis of naturally occurring polyacetylenes via a bis-silylated diyne

Fiandanese, Vito; Bottalico, Daniela; Marchese, Giuseppe; Punzi, Angela

doi:10.1016/j.tet.2006.03.043

Cited by 35 publications

(27 citation statements)

References 25 publications

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“…However, to the best of our knowledge, there is no single example of a complete SCXRD characterization of a furan-based polymer. While some natural furan-based diacetylene (DA) do exist [38][39][40], no attempts to polymerize them have been reported. This seems quite surprising since polydiacetylene (PDA) has attracted tremendous attention for applications in various fields [41,42] due to its unique chromatic [43][44][45][46][47][48][49][50] and semi-conductive properties [51][52][53][54][55][56][57][58][59][60][61].…”

Section: Introductionmentioning

confidence: 99%

Preparation and Single Crystal Structure Determination of the First Biobased Furan-Polydiacetylene Using Topochemical Polymerization

et al. 2019

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Crystal structure elucidations of bio-based polymers provide invaluable data regarding structure-property relationships. In this work, we achieved synthesis and Single Crystal X-ray Diffraction (SCXRD) structural determination of a new furan-based polydiacetylene (PDA) derivative with carbamate (urethane) functionality. Firstly, diacetylene (DA) monomers were found to self-assemble in the crystalline state in such a way that the polymerization theoretically occurred in two different directions. Indeed, for both directions, geometrical parameters for the reactive alignment of DA are satisfied and closely related with the optimal geometrical parameters for DA topochemical polymerization (d(1) = 4.7-5.2 Å, d(2) ≤ 3.8 Å, θ ≈ 45 • ). However, within the axis of hydrogen bonds (HB), the self-assembling monomers display distances and angles (d(1) = 4.816 Å, d(2) = 3.822 Å, θ = 51 • ) that deviate more from the ideal values than those in the perpendicular direction (d(1) = 4.915Å, d(2) = 3.499Å, θ ≈ 45 • ). As expected from these observations, the thermal topochemical polymerization occurs in the direction perpendicular to the HB and the resulting PDA was characterized by SCXRD.

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Section: Introductionmentioning

confidence: 99%

Preparation and Single Crystal Structure Determination of the First Biobased Furan-Polydiacetylene Using Topochemical Polymerization

et al. 2019

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“…This technique has been used previously with Ag I /Pd 0 catalysts, and with K 2 CO 3 /MeOH acting as both a TMS-deprotection reagent and a base for the Sonogashira coupling. [19] We found that a similar approach using Cu I /Pd 0 in the presence of K 2 CO 3 /MeOH or a milder KF/MeOH system was very efficient in the synthesis of aryl diacetylenic alcohols, and for the introduction of eneyne scaffolds. [14a,14d] The Sonogashira coupling of diynes 2c and 2d using KF/ MeOH for one-pot TMS-group removal gave diacetylenes 3c and 3d in high yields, without affecting the ester group (Table 1, entries 3 and 4).…”

Section: Resultsmentioning

confidence: 99%

Towards Isocoumarin‐Fused Enediyne Systems through the Electrophilic Cyclization of Methyl o‐(Buta‐1,3‐diynyl)benzoates

et al. 2015

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“…Consequently, we could apply the same conditions for the coupling of bromoarenes with bis(trimethylsilyl)butadiyne as for the coupling with ethynyltrimethylsilane. Monodesilylation of bis(trimethylsilyl)butadiyne and transformation into an alkynylzinc reagent was described earlier by Frauenrath and co‐workers by using MeLi ⋅ LiBr in Et 2 O, a reagent frequently applied for the monodesilylation of bis(trimethylsilyl)alkynes . The (trimethylsilylbutadiynyl)arenes were protodesilylated by using K 2 CO 3 in methanol.…”

Section: Methodsmentioning

confidence: 99%

“…Monodesilylation of bis(trimethylsilyl)butadiyne and transformation into an alkynylzinc reagent was described earlier by Frauenrath and coworkers by using MeLi·LiBr in Et 2 O, [66,67] ar eagent frequently applied for the monodesilylation of bis(trimethylsilyl)alkynes. [68][69][70][71][72][73][74] The (trimethylsilylbutadiynyl)arenes were protodesilylated by using It should be noted that the trimethylsilyl-protected butadiynylarenes are stable and can be handled without special precautions. However,t he free butadiynylarenes decompose under the influence of heat and/or light.…”

Section: Experimental Section Chemical Reagentsmentioning

confidence: 99%

Quantitative Structure–Retention Relationships for Polycyclic Aromatic Hydrocarbons and their Oligoalkynyl‐Substituted Derivatives

et al. 2017

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Reversed‐phase high‐performance liquid chromatography (RP‐HPLC) has been carried out for a series of unsubstituted polycyclic aromatic hydrocarbons (PAHs) and the corresponding ethynyl, 1,3‐butadiynyl, and 1,3,5‐hexatriynyl derivatives. Theoretical values of the isotropic polarizability and several polarity descriptors have been computed for each compound by using semiempirical models and density functional theory (DFT), with the aim of evaluating linear functions as quantitative structure–retention relationships (QSRRs). The polarity has been described by using either the permanent electric dipole moment, the subpolarity, or a topological electronic index. Three types of partial atomic charges have been used to calculate the subpolarity and a topological index. The choice of the theoretical model, of the polarity descriptor, and of the partial atomic charges is discussed and the resulting QSRRs are compared. Calculating the retention times from the polarizability and the topological electronic index (AM1, PM3, or DFT‐B3LYP/6–31+G(d,p)) gives the best agreement with the experimental values.

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Synthesis of naturally occurring polyacetylenes via a bis-silylated diyne

Cited by 35 publications

References 25 publications

Preparation and Single Crystal Structure Determination of the First Biobased Furan-Polydiacetylene Using Topochemical Polymerization

Preparation and Single Crystal Structure Determination of the First Biobased Furan-Polydiacetylene Using Topochemical Polymerization

Towards Isocoumarin‐Fused Enediyne Systems through the Electrophilic Cyclization of Methyl o‐(Buta‐1,3‐diynyl)benzoates

Quantitative Structure–Retention Relationships for Polycyclic Aromatic Hydrocarbons and their Oligoalkynyl‐Substituted Derivatives

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