133909-96-3

Upstream product

• 585-76-2 m-bromobenzoic acid 
• 5720-05-8 4-methylphenylboronic acid 
• 6952-59-6 3-cyanobromobenzene 
• 192887-48-2 p-MeC₆H₄-MnCl 
• 106-38-7 para-bromotoluene 
• 696-61-7 4-tolylmagnesium chloride 
• 3375-31-3 palladium diacetate 
• 66152-74-7 3-<(trifluoromethanesulfonyl)oxy>benzonitrile 
• 5142-75-6 tri(p-tolyl)bismuth 
• 401-78-5 3-bromo-1-trifluoromethylbenzene 
• 5798-75-4 Ethyl 4-bromobenzoate 
• 402-43-7 p-trifluoromethylphenyl bromide 
• 766-84-7 3-chloro-benzonitrile 
• 66117-64-4 di(p-tolyl)borinic acid 

Downstream Products

• 544694-57-7 4-{4-[(3'-carbamimidoyl-biphenyl-4-ylmethyl)-methanesulfonyl-amino]-phenoxy}-piperidine-1-carboxylic acid tert-butyl ester 
• 644-08-6 4-Methylbiphenyl 
• 1184915-89-6 5-(4'-methyl-biphenyl-3-yl)-1-trityl-1H-tetrazole 
• 1429045-90-8 C₂₅H₂₂N₆S 
• 1429045-87-3 C₂₃H₁₈N₆S 
• 1429045-85-1 C₂₂H₁₆N₆S 
• 1417334-85-0 C₂₁H₁₄N₄OS 
• 1417334-74-7 C₂₃H₁₅N₃O₃S 
• 1417334-67-8 C₂₄H₁₇N₃O₃S 

Relevant academic research and scientific papers

Convenient and efficient Suzuki-Miyaura cross-coupling catalyzed by a palladium/diazabutadiene system

(matrix presented) A Pd(OAc)2/diazabutadiene system has been developed for the catalytic cross-coupling of aryl halides with arylboronic acids. A combination of the diazabutadiene DAB-Cy (1, N,N′-dicyclohexyl-1,4-dizabutadiene) and Pd(OAc)2 was found to form an excellent catalyst for the Suzuki-Miyaura cross-coupling of various aryl bromides and activated aryl chlorides with arylboronic acids.

Synthesis method of substituted biphenyl compound

The invention relates to a synthesis method of a substituted biphenyl compound, which comprises the steps of under the catalysis of 1, 3-bis (2, 6-diisopropyl benzene) imidazole-2-yl subunit] (3-chloropyridyl) palladium dichloride (I I), coupling a Knochel metal reagent and halogenated benzene to obtain the substituted biphenyl compound. Based on the method, the Knochel metal reagent and halogenated benzene are taken as a substrate, PEPPSI-IPr is taken as a catalyst of a coupling reaction, the reaction is rapid, the activity is high, the efficiency and the yield of the coupling reaction are remarkably improved, sensitive groups such as cyano groups and ester groups have good tolerance to the metal reagent, and then the range of the substrate is greatly widened.

Ligand-Promoted Direct C-H Arylation of Simple Arenes: Evidence for a Cooperative Bimetallic Mechanism

A highly efficient catalyst for the direct C-H arylation of simple arenes was developed on the basis of a palladium-diimine complex. The developed catalyst exhibited the highest turnover number reported to date for the direct arylation of benzene due to increased stability provided by the diimine ligand. The reaction was also performed using only 2-3 equiv of simple arenes. Mechanistic studies in combination with kinetic measurements, isotope effect experiments, synthesis of possible intermediates, and stoichiometric reactions suggested that this reaction follows a cooperative bimetallic mechanism.

Amide-ligand-controlled highly para-selective arylation of monosubstituted simple arenes with arylboronic acids

Pd-catalyzed highly para-selective arylations of monosubstituted simple arenes with arylboronic acids to widely existed biaryls have been developed. Inspired by requisite amide-directing groups in reported selective oxidative couplings, amide ligands, especially DMF, are designed and found to be critical for the selectivity control in current arylations.

A cross-coupling synthesis of functionalised biaryls using Knochel-type organozinc reagents and a pyridine enhanced palladium catalyst

A variety of functionalised biaryls were synthesised on the 20-30 mmol scale by using Knochel type organozinc reagents (organozinc reagents prepared from aryl halides, Zn powder and LiCl) catalysed by PEPPSI (a pyridine enhanced palladium catalyst). The protocol enabled the Negishi reactions to proceed in a smooth, rapid and mild way to give the corresponding products in excellent yields (80 ～ 96%). Sensitive functional groups, such as CN and COOEt groups, were tolerated in the coupling reaction.

Efficient phosphine ligands for the one-pot palladium-catalyzed borylation/Suzuki-Miyaura cross-coupling reaction

We report the synthesis of 2-(anthracen-9-yl)-1H-inden-3-yl dicyclohexylphosphine and its use in palladium-catalyzed borylation/Suzuki-Miyaura cross-coupling reaction to prepare a variety of symmetrical and unsymmetrical biaryl compounds in excellent yield. This journal is

Catalytic Decarboxylative Cross-Coupling of Aryl Chlorides and Benzoates without Activating ortho Substituents

The restriction of decarboxylative cross-coupling reactions to ortho-substituted or heterocyclic carboxylate substrates was overcome by holistic optimization of a bimetallic Cu/Pd catalyst system. The combination of a CuI/Me4phen decarboxylation catalyst and a [(MeCN)4Pd](OTf)2/XPhos cross-coupling catalyst enables the synthesis of biaryls from inexpensive aryl chlorides and potassium benzoates regardless of their substitution pattern. Lifting the restriction: A combination of a CuI/Me4phen decarboxylation catalyst and a [(MeCN)4Pd](OTf)2/XPhos cross-coupling catalyst enables the synthesis of biaryls from inexpensive aryl chlorides and potassium benzoates regardless of their substitution pattern (see scheme; FG=functional group). This approach lifts the restriction of decarboxylative cross-coupling reactions to ortho-substituted or heterocyclic carboxylate substrates.

Nickel-catalyzed cross-coupling of diarylborinic acids with aryl chlorides

A highly efficient nickel/triarylphosphine catalyst system, Ni[P(4-MeOPh)3]2Cl2/2P(4-MeOPh)3, has been developed for cross-coupling of diarylborinic acids with a wide range of aryl chlorides. A variety of unsymmetrical biaryl and heterobiaryl compounds with various functional groups and steric hindrance could be obtained in good to excellent yields using 0.5-2 mol % catalyst loadings in the presence of K 3PO4·3H2O in toluene. The high atom economy of diarylborinic acids and cost-effectiveness of the nickel/phosphine catalyst system make the cross-coupling truly practical in the production of biaryl fine chemicals. Usefulness of the nickel/phosphine catalyzed cross-coupling of diarylborinic acids with aryl chlorides has been demonstrated in the development of a scalable and economical process for synthesis of 4′-methyl-2-cyanobiphenyl, Sartan biphenyl.

N-heterocyclic carbene-assisted, Bis(phosphine)nickel-catalyzed cross-couplings of diarylborinic acids with aryl chlorides, tosylates, and sulfamates

Efficient bis(phosphine)nickel-catalyzed cross-couplings of diarylborinic acids with aryl chlorides, tosylates, and sulfamates have been effected with an assistance of N-heterocyclic carbene (NHC) generated in situ from N,N′-dialkylimidazoliums, e.g., N-butyl-N′-methylimidazolium bromide ([Bmim]Br), in toluene using K3PO4·3H2O as base. In contrast to bis(NHC)nickel-catalyzed conventional Suzuki coupling of arylboronic acids, mono(NHC)bis(phosphine)nickel species generated in situ from Ni(PPh3)2Cl2/[Bmim]Br displayed high catalytic activities in the cross-couplings of diarylborinic acids. The structural influences from diarylborinic acids were found to be rather small, while electronic factors from aryl chlorides, tosylates, and sulfamates affected the couplings remarkably. The couplings of electronically activated aryl chlorides, tosylates, and sulfamates could be efficiently effected with 1.5 mol % NiCl2(PPh3)2/[Bmim]Br as catalyst precursor to give the biaryl products in excellent yields, while 3-5 mol % loadings had to be used for the couplings of non- and deactivated ones. A small ortho-substitutent on the aromatic ring of aryl chlorides, tosylates, and sulfamates was tolerable. Applicability of the nickel-catalyzed cross-couplings in practical synthesis of fine chemicals has been demonstrated in process development for a third-generation topical retinoid, Adapalene.

A ligand-free palladium-catalyzed cross-coupling of aryl sulfinates with aryl bromides

A ligand-free Pd-catalyzed cross-coupling of aryl sulfinates with aryl bromides has been developed. A variety of aryl bromides and aryl sulfinates undergo this transformation to yield the desired biaryl in a practical and economical manner. Georg Thieme Verlag Stuttgart New York.