74963-04-5

Upstream product

• 3473-63-0 formamidine acetic acid 
• 82525-12-0 (Z)-3-Methylsulfanyl-2-p-tolyl-propenal 
• 4595-59-9 5-bromopyrimidine 
• 5720-05-8 4-methylphenylboronic acid 
• 104-87-0 4-methyl-benzaldehyde 
• 69153-05-5 1-Methyl-4-((Z)-2-methylsulfanyl-vinyl)-benzene 
• 106-38-7 para-bromotoluene 
• 195062-57-8 p-tolylboronic pinacol ester 
• 289-95-2 PYRIMIDINE 
• 624-31-7 4-tolyl iodide 
• 5720-07-0 4-methoxyphenylboronic acid 
• 2036-41-1 5-methylpyrimidine 
• 31614-66-1 tributyl(p-tolyl)stannane 
• 109299-78-7 pyrimidine 5-boronic acid 

Downstream Products

• 74963-11-4 5-(p-tolyl)-N-phenacylpyrimidinium bromide 

Relevant academic research and scientific papers

Stannylation of Aryl Halides, Stille Cross-Coupling, and One-Pot, Two-Step Stannylation/Stille Cross-Coupling Reactions under Solvent-Free Conditions

Solvent-free protocols for palladium-catalyzed stannylation of aryl halides, Stille cross-coupling, and one-pot, two-step stannylation/Stille cross-coupling (SSC) are reported for the first time. (Het)aryl halides bearing acceptor, donor, as well as sterically demanding substituents are stannylated and/or coupled in high yields. The reactions are catalyzed by conventional palladium(II) acetate/PCy3 [Pd(OAc)2/PCy3] under air, using available base CsF, and without the use of high purity reagents. The developed synthetic procedures are versatile, robust, and easily scalable. The absence of solvent, and the elimination of isolation procedures of aryl stannanes makes the SSC protocol simple, step economical, and highly efficient for the synthesis of biaryls in a one-pot two-step procedure.

Cyrene as a Bio-Based Solvent for the Suzuki-Miyaura Cross-Coupling

The Suzuki-Miyaura (SM) cross-coupling is the most broadly utilized Pd-catalyzed C-C bond-forming reaction in the chemical industry. A large proportion of SM couplings employ dipolar aprotic solvents; however, current sustainability initiatives and increasingly stringent regulations advocate the use of alternatives that exhibit more desirable properties. Here we describe the scope and utility of the bio-derived solvent Cyrene in SM cross-couplings and evaluate its suitability as a reaction medium for this benchmark transformation from discovery to gram scale.

Synthesis of zwitterionic palladium complexes and their application as catalysts in cross-coupling reactions of aryl, heteroaryl and benzyl bromides with organoboron reagents in neat water

N-(3-Chloro-2-quinoxalinyl)-N′-arylimidazolium salts (aryl = 2,6-diisopropylphenyl [HL1Cl]Cl, aryl = mesityl [HL2Cl]Cl) have been synthesized by treating 2,3-dichloroquinoxaline with the corresponding N′-arylimidazole in neat water. Facile reactions of these imidazolium salts with Pd(PPh3)4 and Pd2(dba)3/PPh3 (dba = dibenzyledene acetone) at 50 °C have afforded zwitterionic palladium(ii) complexes [Pd(HL1)(PPh3)Cl2] (I) and [Pd(HL2)(PPh3)Cl2] (II) in excellent yields. I and II have been tested for their ability to catalyze Suzuki-Miyaura cross coupling (SMC) reactions in neat water/K2CO3 and are found to be highly active for carrying out these reactions between aryl bromides and organoboron reagents. Furthermore, the scope of the catalyst I was also examined by employing (hetero)aryl bromides, hydrophilic aryl bromides, benzyl bromides and various organoboron reagents. More than 80 aryl/benzyl bromide-arylboronic acid combinations were screened in neat water/K2CO3 and it was found that I was a versatile catalyst, which produced biaryls/diarylmethanes in excellent yields. A TON of 82 000 was achieved by using I. Studies on the mechanism have also been carried out to investigate the involvement of carbene complexes in the catalytic path. Poison tests and a two-phase test were also conducted and the results are reported.

Oxygen-promoted Pd/C-catalyzed Suzuki-Miyaura reaction of potassium aryltrifluoroborates

A simple and highly efficient protocol has been developed for the Pd/C-catalyzed ligand-free Suzuki-Miyaura reaction of potassium aryltrifluoroborates. In this catalytic system, the results demonstrate that oxygen plays a positive role in the cross-coupling reaction. In addition, this catalytic system could be successfully applied to synthesize biaryl compounds containing a carbazole moiety and the catalyst was recycled seven times without significant loss of catalytic activity.

Metal-free arylation of pyrimidines through a photochemical process

Pyrimidinyl and pyrazinyl radicals were generated under moderate energetic irradiation conditions (UVA), and proved to be prompt to undergo C-C bond formation processes. Hetero-biaryl derivatives were obtained in good to high yields with highly interesting functional group selectivities. Bis hetero-biaryls were also easily accessible leading to original compounds, ready for further transformations. Experiments supporting radical processes have been reported.

In situ-generated nano-palladium-catalyzed ligand-free Suzuki-Miyaura reaction of potassium aryltrifluoroborates at room temperature

A mild and simple protocol is described for the palladium-catalyzed ligand-free Suzuki-Miyaura reaction of potassium aryltrifluoroborates in aqueous ethanol at room temperature. Palladium nanoparticles are generated in situ in the reaction and demonstrate high activity towards a wide range of aryl bromides and potassium aryltrifluoroborates, providing biphenyls in good to excellent yields. Interestingly, only 1 equiv of K2CO3 is used in this catalytic system. Moreover, the key biaryl intermediate of 2-cyano-4′-methylbiphenyl within valsartan is prepared in a 95% yield after 2 h.

2-(diphenylphosphino)pyridine platinum (I) and palladium (I) complex as an efficient binuclear catalyst for Suzuki-Miyaura coupling reaction in water under mild reaction conditions

Binuclear complex of platinum (I) and palladium (I) showed superior activity in Suzuki-Miyaura coupling reaction of aryl halides with arylboronic acids compared to the sole palladium or platinum species. The catalyst showed good tolerance in water and coupling reactions were performed in water as a green solvent. Aryl iodides were reacted at room temperature and the reactions of aryl bromides were performed at 60 °C.

AMVN-initiated expedient synthesis of biaryls by the coupling reaction of unactivated arenes and heteroarenes with aryl iodides

The role of radical initiators AMVN and AIBN has been studied in the potassium tert-butoxide mediated biaryl coupling reaction of aryl iodides with unactivated arenes. Radical initiator AMVN promoted carbon-carbon bond formation expeditiously from aryl iodide having various groups such as amino, methoxy, fluoro, methyl, and trifluoromethyl and arenes in the presence of potassium tert-butoxide (4 equiv.) at 110 °C in 2-5 h. Substituted arenes such as toluene, xylene, anisole, and fluorobenzene also proceeded to form biaryls under AMVN-initiated reaction conditions. Moreover naphthalene, pyridine, pyrimidine, and pyridazine also coupled with aryl iodides and produced biaryls in 41-82% yields. It seems that AMVN initiates the formation of the aryl radical, which enters the radical chain reaction. The generated aryl radical may combine with the arene leading to a biaryl radical, which upon protonation gives the biphenyl radical anion and tert-butanol. The biphenyl radical anion finally reacts with the aryl iodide generating the aryl radical and thus completes the radical chain reaction with concomitant release of biphenyl.

Suzuki-miyaura cross-coupling under solvent-free conditions

A solvent-free reaction protocol for Suzuki-Miyaura cross-couplings was developed. (Hetero)aryl bromides and chlorides are coupled with pinacol arylboronates in high yields. The reaction is catalyzed by conventional bis(triphenylphosphine)palladium(II) chloride [(PPh3) 2PdCl2] and/or palladium(II) acetate/SPhos [Pd(OAc) 2/SPhos] under air. Copyright

Expanded ring diaminocarbene palladium complexes: Synthesis, structure, and Suzuki-Miyaura cross-coupling of heteroaryl chlorides in water

A series of new 6- and 7-membered N-heterocyclic carbene (NHC) complexes of palladium (NHC)Pd(cinn)Cl (cinn = cinnamyl = 3-phenylallyl) were synthesized and characterized structurally in the solid state. The influence of ring size (5, 6 or 7) and bulkiness of N-aryl substituents (Mes = 2,4,6-trimethylphenyl, or Dipp = 2,6-diisopropylphenyl) in carbenes on palladium catalysed Suzuki-Miyaura cross-coupling was revealed. Due to the unique stereoelectronic properties of expanded ring NHCs, a versatile, highly efficient green protocol of coupling of heteroaromatic chlorides and bromides with boronic acids has been developed. High quantitative yields of biaryls were achieved with water as solvent, under air, using low catalyst and phase transfer agent loadings, and with mild and environmentally benign base NaHCO3. The Royal Society of Chemistry 2013.