17763-78-9

Upstream product

• 66107-30-0 4-bromophenyl trifluoromethanesulfonate 
• 100-58-3 phenylmagnesium bromide 
• 29540-84-9 4-chlorophenyl trifluoromethanesulfonate 
• 934-56-5 trimethyl(phenyl)stannane 
• 98-80-6 phenylboronic acid 
• 106-48-9 4-chloro-phenol 
• 960-16-7 tributylphenylstannane 

Downstream Products

• 92-92-2 biphenyl-4-carboxylic acid 
• 2920-38-9 4-cyano-1,1'-biphenyl 
• 92-52-4 biphenyl 
• 96372-83-7 1-([1,1′-biphenyl]-4-yl)piperidine 
• 92-67-1 4-phenylalanine 
• 82745-24-2 (4-biphenylyl)-p-tolyl sulfone 
• 110966-08-0 N,N-Diisopropyl-3-phenylaniline 
• 110966-09-1 N,N-diisopropyl-[1,1'-biphenyl]-4-amine 
• 808142-70-3 5-methyl-2-(4-phenylphenyl)pyridine 
• 1212022-79-1 (5R,7aR)-5-(4-phenylbenzyl)hexahydropyrrolizin-3-one 
• 324-74-3 4-fluoro-biphenyl 
• 2367-22-8 3-fluorobiphenyl 
• 57477-98-2 3-biphenyl-4-yl-3-oxopropionic acid ethyl ester 
• 67747-74-4 1-([1,1'-biphenyl]-4-yl)-3-(4-methoxyphenyl)prop-2-yn-1-one 

Relevant academic research and scientific papers

Solvent coordination to palladium can invert the selectivity of oxidative addition

Reaction solvent was previously shown to influence the selectivity of Pd/PtBu3-catalyzed Suzuki-Miyaura cross-couplings of chloroaryl triflates. The role of solvents has been hypothesized to relate to their polarity, whereby polar solvents stabilize anionic transition states involving [Pd(PtBu3)(X)]- (X = anionic ligand) and nonpolar solvents do not. However, here we report detailed studies that reveal a more complicated mechanistic picture. In particular, these results suggest that the selectivity change observed in certain solvents is primarily due to solvent coordination to palladium. Polar coordinating and polar noncoordinating solvents lead to dramatically different selectivity. In coordinating solvents, preferential reaction at triflate is likely catalyzed by Pd(PtBu3)(solv), whereas noncoordinating solvents lead to reaction at chloride through monoligated Pd(PtBu3). The role of solvent coordination is supported by stoichiometric oxidative addition experiments, density functional theory (DFT) calculations, and catalytic cross-coupling studies. Additional results suggest that anionic [Pd(PtBu3)(X)]- is also relevant to triflate selectivity in certain scenarios, particularly when halide anions are available in high concentrations.

Rapid Access to Bi- and Tri-Functionalized Dibenzofurans and their Application in Selective Suzuki–Miyaura Cross Coupling Reactions

Syntheses of 1,2-, 1,3-, 1,4-, 1,8-, 2,4-, 3,4-, 4,8-, 1,2,4-, 1,2,8- and 1,3,4-functionalized dibenzofurans in few steps with good to excellent yields starting from dibenzofuran-1-ol or -4-ol are presented. These rapidly accessible bi- or tri-functionalized building blocks are of great interest for the synthesis of bioactive substances or functional material development. Furthermore, for intermediates containing both a bromine and a triflate moiety, a selective mono-substitution by means of Suzuki–Miyaura reaction (SMR) is described.

Solvent effect on palladium-catalyzed cross-coupling reactions and implications on the active catalytic species

Suzuki coupling of the bifunctional substrate 1 using [Pd 2(dba)3]/PtBu3 gives selectivity for C-Cl in nonpolar solvents but for C-OTf in polar solvents. The results of computational and experimental studies suggest that the catalytically active species in polar solvents under conditions employing coordinating additives is inconsistent with monoligated [Pd(PtBu3)]. Instead, the data are consistent with an anionic palladium complex as the active species.

Metal-catalyzed amination of organic sulfonates to organic amines

A process of preparing an organic amine having at least one unsaturated group, such as an arylamine, involving contacting an unsaturated organic sulfonate, such as an aryl sulfonate, with a reactant amine, such as an alkyl or aryl amine, in the presence of a base and a transition metal catalyst under reaction conditions. The transition metal catalyst contains a Group 8 metal and a chelating ligand, for example a Group 15-substituted arylene or Group 15-substituted metallocene, such as 1,1'-bis(diphenylphosphino)-2,2'-binaphthyl or 1,1'-bis(diphenylphosphino)-ferrocene, respectively. The aryl sulfonate can be prepared from a phenol and sulfonating agent.

Control of reactive site in Palladium-Catalyzed grignard Cross-Coupling of arenes containing both bromide and triflate

Reaction of 4-bromophenyl triflate (1) with phenylmagnesium bromide in the presence of 5 mol % of PdCl2(dppp) gave 97% yield of 4-bromobiphenyl (2a), which was formed by selective replacement of triflate in 1 by phenyl. On the other hand, bromide in 1 was substituted with the phenyl Grignard reagent selectively by use of PdCl2(meo-mop)2 to give 4-biphenyl triflate (3a) in high yield. The selective substitution was demonstrated to take place at the oxidative addition step to a palladium(0) species in a stoichiometric reaction of 1 with palladium(0) phosphine complexes.