Pd-Catalyzed Decarboxylative Coupling of Propiolic Acids: One-Pot Synthesis of 1,4-Disubstituted 1,3-Diynes via Sonogashira−Homocoupling Sequence

Park, Jihye; Park, Eonjeong; Kim, Aejin; Park, Seul‐A; Lee, Youngil; Chi, Ki‐Whan; Jung, Young Hoon; Kim, In Su

doi:10.1021/jo200096x

Cited by 85 publications

(40 citation statements)

References 48 publications

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“…The preparation for this compound was according to a similar procedure described in the literature. 21 Synthesis of Compound 5. A solution of hexyl bromide (1.05 g, 6.36 mmol) in anhydrous acetone (5 mL) was added dropwise into a mixture of compound 6 (1.5 g, 6.41 mmol) and potassium carbonate (0.8 g, 5.8 mmol) in anhydrous acetone (15 mL) at 60°C.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Unimolecular Photopolymerization of High-Emissive Materials on Cylindrical Self-Assemblies

Zhu

Sanders

et al. 2015

Macromolecules

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We report a novel self-assembly pathway from a bis(imidazolyl) diphenyl−diacetylene (DPDA) compound as a realization of self-templated photopolymerization with high polymerization degrees. The work takes advantage of a cylindrical self-assembly that strengthens the preorganization of the diphenyl−diacetylene moiety at the single molecular level. On this basis, photopolymerization of DPDA can be conducted smoothly to form high-molecular-weight polydiphenyl diacetylene. Such a cylindrical self-assembly is highly dependent on molecular structure, and control studies show that only oligomers can be formed on random self-assemblies from a monoimidazolyl or nonimidazolyl diphenyl−diacetylene compound. Moreover, the cylindrical self-assembly based systems bear aggregation-induced emission enhancement characteristics and are solution processable. The leading thin-film could afford a selectively tunable function in luminescent micropatterns. ■ INTRODUCTIONAs compared with most conventional diacetylenes with alkyl chains directly connected to the butadiyne unit, the diphenyl− diacetylene (DPDA) moiety with aryl groups attached to the butadiyne has an extended π-conjunction and introduces a large intermolecular stacking tendency. These features generally allow the mesogen as well as the corresponding polydiacetylene species to exhibit more versatile optoelectronic properties, 1−3 implying great interest for their potential exploitation in high birefringence materials, modern display technologies, luminescent emitting diodes, and ideal prototype for molecular devices, etc. 4 Since the first report of diacetylene polymerization in the solid state by Wegner, 5 it has been widely accepted that molecular preorganization is a crucial factor to achieve highly efficient topochemical polymerizations of diacetylene. To drive such an effective polymerization on a diphenyl−diacetylene (DPDA) monomer seems to be difficult, simply because the bulky size of the neighboring phenyl rings in DPDA greatly hampers the minimum movement of the butadiyne moiety. The past decades have witnessed extensive progress in developing many key strategies, based on grafting diacetylene monomers on surface-aligned films or introducing functional groups on the diacetylene monomers to control their aggregation and crystallization, followed by thermal or photochemical polymerization. 6 However, only the formation of oligomers, or even no reaction at all, is observed in most of cases of DPDAs. 7 Gelation and monolayer strategies may somehow promote the polymerization of DPDAs, 8 but they lack solution processability, which will limit large-scale development. A straightforward approach for enhancing the polymerization degree of DPDA in a solution processable manner remains a challenge.Structural-dependent ordered self-assembled nanoarchitectures formed in a certain solvent environment generally show properties distinct from those of their individual constituent molecules, 9 and can even be helpful for improving the chemical reaction behavior. 10 In particular, s...

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Section: ■ Experimental Sectionmentioning

confidence: 99%

Unimolecular Photopolymerization of High-Emissive Materials on Cylindrical Self-Assemblies

Zhu

Sanders

et al. 2015

Macromolecules

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“…Although 1,4‐diarylbutadiyne is the key intermediate and can be obtained from the aryl iodide, the direct formation of desired product 4 from the aryl iodide failed. The previously reported conditions did not give the cyclized product 4 .…”

Section: Resultsmentioning

confidence: 99%

Copper‐Catalyzed Synthesis of Amino‐Substituted Polycyclic Aromatic Hydrocarbons by the Sequential Reaction between Aryl Alkynyl Carboxylic Acids and Amines

et al. 2015

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Amino-substitutedp olycyclic aromatic hydrocarbons were obtained by the reaction between aryl alkynyl carboxylic acids and amines in the presence of ac opper catalyst. The hydrocarbonsw ere obtained in good yield with-out the need to isolate the 1,4-diaryl-1,3-butadiyne intermediate. The best result was obtained using ac ombination of CuCl and Cu(OTf) 2 ,a nd the reactions of cyclic anda cyclic secondary amines afforded the desired products.Scheme1.Synthesis of amino-substitutednaphthalenes.[a] J.

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“…In 2011, Park et al [114] reported a Pd-catalyzed decarboxylative coupling (see Chapter 3 for further details on decarboxylative coupling reactions) of propiolic acids, which involves a Sonogashira-Hagihara homocoupling sequence. Their reaction represents a new approach to the synthesis of 1,3-diynes, besides the classical approaches, which include Glaser coupling, Chodkiewicz-Cadiot coupling, Rossi's protocol, and Lei's protocol.…”

Section: Arylations With the Sonogashira-hagihara Reactionmentioning

confidence: 99%

“…Figure 1.33 The Sonogashira-Hagihara reaction variant of Fabrizi et al [113] with arenediazonium salts.Figure 1.34 The Pd-catalyzed decarboxylative coupling as described by Park et al[114].…”

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confidence: 99%

Cross‐Coupling Arylations: Precedents and Rapid HistoricalReview of the Field

2014

Catalytic Arylation Methods

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Pd-Catalyzed Decarboxylative Coupling of Propiolic Acids: One-Pot Synthesis of 1,4-Disubstituted 1,3-Diynes via Sonogashira−Homocoupling Sequence

Cited by 85 publications

References 48 publications

Unimolecular Photopolymerization of High-Emissive Materials on Cylindrical Self-Assemblies

Unimolecular Photopolymerization of High-Emissive Materials on Cylindrical Self-Assemblies

Copper‐Catalyzed Synthesis of Amino‐Substituted Polycyclic Aromatic Hydrocarbons by the Sequential Reaction between Aryl Alkynyl Carboxylic Acids and Amines

Cross‐Coupling Arylations: Precedents and Rapid HistoricalReview of the Field

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