Heteroacene Synthesis through C−S Cross‐Coupling/5‐<i>endo</i>‐<i>dig</i>Cyclization

Oechsle, Peter; Flörke, Ülrich; Egold, Hans; Paradies, Jan

doi:10.1002/chem.201603737

Cited by 17 publications

(7 citation statements)

References 49 publications

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“…Recently, Paradies and coworkers 46 reported a highly efficient one-step synthesis of sulfur-containing heteroacenes through palladium-catalyzed C-S cross-coupling of bis-alkynes with thioacetate as a hydrogen sulfide surrogate (Scheme 6). The eight C-S bonds in compound 18 could be synthesized in a single step.…”

Section: S-bridged Lhas Synthesized By Heteroannulationmentioning

confidence: 99%

Exploration of Syntheses and Functions of Higher Ladder-type π-Conjugated Heteroacenes

Cai

Awais

Zhang

et al. 2018

Chem

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Ladder-type heteroacenes with well-defined structures and highly planar and delocalized p-electrons are an important class of materials for potential applications in organic electronics. The incorporation of heteroatoms into the ladder backbone allows for tuning optical-electronic properties and crystal structures in the solid state. Significant progress in synthesis and physical studies of a number of fascinating ladder molecules has been achieved. This review discusses progression in synthetic methods, structural characterization, and applications of ladder-type heteroacenes.

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Section: S-bridged Lhas Synthesized By Heteroannulationmentioning

confidence: 99%

Exploration of Syntheses and Functions of Higher Ladder-type π-Conjugated Heteroacenes

Cai

Awais

Zhang

et al. 2018

Chem

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“…We and others have shown that silyl thiol, [ 35 ] thiourea [ 36 ] or potassium thioacetate [ 37 ] offer the unique access to diaryl sulfide derivatives. [ 36,38–42 ]…”

Section: Entrya) X Y Mnb) Mwb) Mw/mn Dpn Equiv 2 Mol% Cat G Mol−1 mentioning

confidence: 99%

“…From earlier studies in our group, we knew that the electron‐rich [Pd( o Tol 3 P) 2 ] complex in combination with the bis(diphenylphosphino)ferrocene ligand (dppf) performed best in the CS cross coupling to form diaryl sulfides. [ 38–40 ] Accordingly, we turned out attention to the optimization of the H 2 S‐surrogate. Whereas thiourea [ 36 ] was inactive in the polycondensation, potassium thioacetate (KSAc, 2 ) was active in the conversion of 1 to polymeric material in the presence of 2 mol% Pd‐catalyst ( Table 1 entries 1–6).…”

Section: Entrya) X Y Mnb) Mwb) Mw/mn Dpn Equiv 2 Mol% Cat G Mol−1 mentioning

confidence: 99%

Palladium‐Catalyzed Polycondensation for the Synthesis of Poly(Aryl)Sulfides

Hou

Oechsle

Kuckling

et al. 2020

Macromol. Rapid Commun.

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the sulfur atom in one transformation is the most desirable process, however, such a reaction is yet unprecedented. A solution to this shortcoming may be the use of hydrogen sulfide surrogates in CS cross couplings to access poly(phenyl)sulfide derivatives according to a polycondensation reaction. We and others have shown that silyl thiol, [35] thiourea [36] or potassium thioacetate [37] offer the unique access to diaryl sulfide derivatives. [36,[38][39][40][41][42] We here report the synthesis of poly(phenyl)sulfide and so far unprecedented poly(thiophene)sulfide through palladium catalyzed CS bond forming polycondensation.Poly (1,4-phenyl)sulfide is insoluble in organic solvents. Therefore, we turned our focus to alkyl-substituted phenylene derivatives to provide enhanced solubility with the aim to investigate the palladium catalyzed polycondensation reaction. 1,4-Dibromo-2,5-bis((2-ethylhexyl)oxy)benzene (1) was synthesized according to literature procedures [43] and was reacted with palladium(0) sources and hydrogen sulfide surrogates.From earlier studies in our group, we knew that the electron-rich [Pd(oTol 3 P) 2 ] complex in combination with the bis(diphenylphosphino)ferrocene ligand (dppf) performed best in the CS cross coupling to form diaryl sulfides. [38][39][40] Accordingly, we turned out attention to the optimization of the H 2 S-surrogate. Whereas thiourea [36] was inactive in the polycondensation, potassium thioacetate (KSAc, 2) was active in the conversion of 1 to polymeric material in the presence of 2 mol% Pd-catalyst (Table 1 entries 1-6). We identified impurities of the polymer after workup, which consisted according to 31 P NMR of phosphine and catalyst decomposition products. Attempted column chromatography did not lead to any improvement, so that we were not able to determine the yields of the reactions. However, NMR-spectroscopy, mass spectrometry and GPC analysis clearly show the synthesis of the poly(phenyl) sulfide polymer. The polymerization reactions displayed strong dependency on the ratio of 2 and the aryl halide. The optimum was determined to 0.94 equivalents (entry 2) as judged from the molecular weights. Such behavior is common for polycondensation reactions and optimization is required for new batches of coupling partners. Next, we studied the impact of catalyst loading on the polymerization. It was found that highest molecular weight was obtained in the presence of 10 mol% [Pd(oTol 3 P) 2 ]/dppf. However, the number average molecular weight (M n ) and the PDI were not dramatically affected by higher catalyst loadings (compare entries 2, 7 and 8 with 2, 4, and 10 mol%). Therefore, we decided to further optimize the reaction with 2 mol% of the palladium complex. Lithium salts The palladium-catalyzed CS cross coupling reaction is investigated as a novel efficient tool for the synthesis of poly(phenyl)sulfide derivatives. The reaction proceeds through the polycondensation of dibromo arenes with a H 2 S-surrogate to yield poly(aryl)sulfides. The reaction is generalized by the sy...

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“…In this regards, we are reporting a new complex of Cu I on modified boehmite nanoparticles as efficient and reusable catalyst for the synthesis of sulfides and diaryl ethers via C−S and C−O cross coupling reactions. Because sulfides and diaryl ethers are starting material for the synthesis of organic compounds, drugs, and biological materials . Also, sulfides are starting materials for the synthesis of sulfoxides and sulfones …”

Section: Introductionmentioning

confidence: 99%

“…Because sulfides and diaryl ethers are starting material for the synthesis of organic compounds, drugs, and biological materials. [46][47][48][49][50][51][52][53][54][55] Also, sulfides are starting materials for the synthesis of sulfoxides and sulfones. [56]…”

Section: Introductionmentioning

confidence: 99%

New Complex of Copper on Boehmite Nanoparticles as Highly Efficient and Reusable Nanocatalyst for Synthesis of Sulfides and Ethers

Ghorbani‐Choghamarani

Heidarnezhad

Tahmasbi

2019

ChemistrySelect

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Boehmite is a cubic orthorhombic structure of aluminum oxide hydroxide, which prepared via addition of sodium hydroxide solution to an aluminum nitrate solution at room temperature. In this work, the surface of boehmite nanoparticles (BNPs) modified by 3‐choloropropyltrimtoxysilane (3‐CPTMS), then reacted with N,N,N′,N′‐tetraethyldiethylentriamine (TEDETA). Eventually, CuI immobilized on modified boehmite (CuI‐TEDETA@BNPs). Structure of this catalyst was characterized using FT‐IR, TEM, SEM, EDS, TGA, and AAS techniques. Finally, the catalytic activity of CuI‐TEDETA@BNPs was studied for the synthesis of ethers and sulfides. All ethers and sulfides were obtained in high yields, which reveals the high activity of described catalyst. This catalyst was reused for several times without significant loss of its catalytic efficiency. Recovered catalyst was characterized by SEM and FT‐IR techniques, which shown a good agreement with fresh catalyst. Also, heterogeneity and stability of CuI‐TEDETA@BNPs confirmed by hot filtration test.

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Heteroacene Synthesis through C−S Cross‐Coupling/5‐endo‐digCyclization

Cited by 17 publications

References 49 publications

Exploration of Syntheses and Functions of Higher Ladder-type π-Conjugated Heteroacenes

Exploration of Syntheses and Functions of Higher Ladder-type π-Conjugated Heteroacenes

Palladium‐Catalyzed Polycondensation for the Synthesis of Poly(Aryl)Sulfides

New Complex of Copper on Boehmite Nanoparticles as Highly Efficient and Reusable Nanocatalyst for Synthesis of Sulfides and Ethers

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