16939-08-5

Upstream product

• 872-31-1 3-Bromothiophene 
• 16419-60-6 2-Methylphenylboronic acid 
• 6165-69-1 Thien-3-ylboronic acid 
• 95-46-5 2-methylphenyl bromide 
• 10486-61-0 3-thienyl iodide 
• 33872-80-9 o-tolyl magnesium chloride 
• 529-27-1 2-methylphenylhydrazine 
• 95-49-8 2-methylchlorobenzene 
• 7029-31-4 bis(2-methylphenyl)zinc 
• 17249-80-8 3-chlorothiophene 

Downstream Products

• 99902-04-2 2-(3'-thiophene)benzyl bromide 
• 99902-03-1 2-(thien-3-yl)benzaldehyde 

Relevant academic research and scientific papers

Pd-NHCs Enabled Suzuki-Miyaura Cross-Coupling of Arylhydrazines via C–N Bond Cleavage

We describe a highly efficient protocol for cross-coupling of phenylhydrazines with arylboronic acids by Pd-NHCs under aerobic reaction condition. A series of well-defined Pd-NHCs complexes were evaluated and the relationship between the structure and the catalytic properties was investigated. It was disclosed that the Pd-PEPPSI-IPr proved to be the robust precatalyst, providing access to a range of (hetero)biaryls in good to excellent yields.

Non-Directed Cross-Dehydrogenative (Hetero)arylation of Allylic C(sp3)?H bonds enabled by C?H Activation

Herein, we report the selective, non-directed and cross-dehydrogenative coupling of allylic C(sp3)?H bonds with C(sp2)?H bonds of (hetero)arenes. The methodology employs olefins and (hetero)arenes which are abundantly available chemical feedstocks, and could be applied in late-stage functionalization reactions of pharmaceuticals. Furthermore, the system exclusively delivers the allylic C?C coupling products highlighting the preservation of the olefin substitution pattern for further derivatization.

Air-Stable Dinuclear Iodine-Bridged Pd(I) Complex - Catalyst, Precursor, or Parasite? the Additive Decides. Systematic Nucleophile-Activity Study and Application as Precatalyst in Cross-Coupling

Dinuclear Pd(I) complexes were recently shown to potentially adopt various possible roles in catalysis, being capable of functioning as catalyst via dinuclear catalysis cycles, precatalyst for Pd(0), or inhibitor. This report examines the factors that control the mechanistic role in catalysis. Our data suggest that the transformation to Pd(0) occurs via nucleophile-induced fragmentation of Pd(I)-Pd(I). A systematic study examining the nucleophilicity of additive versus activity was undertaken that revealed the minimum nucleophilicity necessary to activate two structurally very similar Pd(I) dimers, [Pd(μ-X)(PtBu3)]2 (X = I or Br). While the more labile bromine-bridged Pd(I) dimer is converted to Pd(0) with nucleophiles N ≥ 10.5, the iodine-bridged analogue requires N ≥ 16.1 (N according to Mayrs scale). Too strong nucleophiles generate a high concentration of unstable monoligated Pd(0) rapidly, leading to Pd loss (i.e., Pd black). On the other hand, careful tuning of nucleophilicity allows for a controlled release of well-defined Pd(0) species. These insights have led to the first application of the air-stable and previously thought unreactive iodine-bridged dimer [Pd(μ-I)(PtBu3)]2 as a precatalyst for monoligated Pd(0) in cross-coupling reactions. The reactions were performed without exclusion of oxygen-all reagents were handled in air without special precautions. Highly efficient Kumada couplings of aryl iodides and bromides were achieved in 5 min at room temperature.

Synthesis of heteroaryl compounds through cross-coupling reaction of aryl bromides or benzyl halides with thienyl and pyridyl aluminum reagents

An efficient method for synthesis of useful biaryl building blocks containing 2-thienyl, 3-thienyl, 2-pyridyl, and 3-pyridyl moieties was provided through cross-coupling reactions of aryl bromides or benzyl halides with heteroaryl aluminum reagents in the presence of Pd(OAc)2 and (o-tolyl)3P. The coupling reaction also worked efficiently with heteroaryl bromides affording series of heterobiaryl compounds. The reaction of phenylbromide with in situ prepared 3-pyridyl aluminum was demonstrated to afford the product 8a in high yield. Additionally, the catalytic system was also suited well for the coupling reaction of benzyl halides with pyridyl aluminum reagents to afford series of pyridyl-arylmethane.

General and highly efficient fluorinated-N-heterocyclic carbene-based catalysts for the palladium-catalyzed Suzuki-Miyaura reaction

A general and highly efficient trifluoromethylated-N-heterocyclic carbene (NHC)-based catalyst for the palladium-catalyzed Suzuki-Miyaura reaction was reported. In the presence of the catalyst, reactions of non-activated aryl chlorides and triflates with aryl boronic acids occurred at room temperature with good to excellent yields (63-98%). In addition, catalysts generated from a combination of Pd(OAc)2/imidazolium salt 6a is not only effective for the coupling of heteroaryl boronic acid with aryl halides and heteroaryl halides, but also efficient for coupling of other heteroaryl halides and heteroaryl boronic acids. Finally, the catalyst is highly effective for Suzuki-Miyaura reaction of aryl bromides and chlorides with 0.01-0.1 mol % loading if the temperature was raised at refluxed THF/H2O.

Highly active and recyclable silica gel-supported palladium catalyst for mild cross-coupling reactions of unactivated heteroaryl chlorides

Silica gel-supported β-ketoiminatophosphane-Pd complex (Pd@SiO 2) was shown to be a highly active and long-lived catalyst for aqueous Suzuki, Stille and Sonogashira coupling reactions of heteroaryl chlorides. A wide range of heteroaryl chlorides could be efficiently coupled with different nucleophilic partners in the presence of only 0.5 mol% catalyst and under mild conditions. This is one of the most powerful heterogeneous catalysts for the couplings of diverse heteroaryl chlorides. Furthermore, the catalyst could be reused with almost consistent activity. The Royal Society of Chemistry 2010.

Expanded heterogeneous Suzuki-Miyaura coupling reactions of aryl and heteroaryl chlorides under mild conditions

A mesoporous LTA zeolite (MP-LTA)-supported palladium catalyst was developed for the highly efficient Suzuki-Miyaura reaction of aryl and heteroaryl chlorides. The couplings of various aryl chlorides with arylboronic acids in aqueous ethanol were efficiently achieved in the presence of 1.0 mol% of the catalyst. Furthermore, the scope of this catalyst was extended to the coupling of heteroaryl chlorides. Regardless of the substituents, all of the coupling reactions were very clean and highly efficient under mild heating. It shows that our catalyst is one of the most powerful heterogeneous catalysts for the coupling of a wide range of aryl and heteroaryl chlorides. The catalyst could be repetitively used at least 10 times without a significant loss of its catalytic activity. Compared to mesoporous SBA-15 and MCM-41 materials, the MP-LTA support proved to be very stable and robust to prevent degradation upon reuse.

Palladium/tetraphosphine catalyzed suzuki cross-coupling of heteroarylboronic acids with aryl halides

(Chemical Equation Presented) cis,cis,cis-1,2,3,4- Tetrakis(diphenylphosphinomethyl)cyclopentane/[PdCl(C3H 5)]2 efficiently catalyses the Suzuki reaction of heteroarylboronic acids with aryl bromides and also the coupling of arylboronic acids with heteroaryl bromides. The coupling of thiophene- or benzothiopheneboronic acids, furan- or benzofuranboronic acids and 3-pyridineboronic acid with a variety of aryl bromides gave the corresponding coupling products in good yields. However, in most cases, better results in terms of ratio substrate/catalyst were obtained for the reverse reaction using heteroaryl bromides with arylboronic acids.