56692-73-0

Upstream product

• 98910-57-7 2-methoxyphenyl mesylate 
• 108-67-8 1,3,5-trimethyl-benzene 
• 576-83-0 2,4,6-trimethylphenyl bromide 
• 5720-06-9 2-Methoxyphenylboronic acid 
• 77408-43-6 2,4,6-trimethylphenyl 2-methoxybenzoate 

Relevant academic research and scientific papers

Iron catalysis for the synthesis of ligands: Exploring the products of hydrophosphination as ligands in cross-coupling

Catalytic hydrophosphination is a useful technique for the synthesis of phosphines, however, the phosphine products have been little exploited as ligands in catalysis. We have selected three phosphines prepared by iron catalyzed hydrophosphination and used them as ligands in a series of cross-coupling reactions: Heck, Suzuki-Miyaura and Buchwald-Hartwig. Rather than limit the chemistry to simple cross-coupling partners which are almost guaranteed to perform well in these transformations, industrially relevant substrates which are challenging from and electronic and/or steric perspective, along with substrates which contain several heteroatoms, were explored in order to gauge the true potential of these phosphine ligands.

An efficient indenyl-derived phosphine ligand for the Suzuki-Miyaura coupling of sterically hindered aryl halides

An air-stable aryl substituted indenyl phosphine used in combination with Pd(OAc)2 provides a highly efficient catalyst for the Suzuki-Miyaura cross-coupling reaction of sterically hindered aryl halides with aryl boronic acids.

An efficient and reusable palladium catalyst supported on a rasta resin for Suzuki-Miyaura cross-couplings

A short and efficient synthesis of a heterogeneous palladium catalyst supported on a rasta resin bearing diphenylphosphanyl ligands is reported. This catalyst was used successfully for Suzuki-Miyaura reactions of aryl bromides in the presence of only 0.25 milli-equiv. of supported palladium. The catalyst was reused several times with no loss of efficiency, and the amount of palladium leached in the reaction medium is extremely low ( 1 % of the initial amount). An efficient heterogeneous palladium catalyst supported on a rasta resin bearing diphenylphosphanyl groups is reported. The catalyst was successfully used for Suzuki-Miyaura reactions of aryl bromides in the presence of only 0.25 milli-equiv. of supported palladium, it can be used at least five times, and the palladium leaching is very low ( 1 % of the initial amount). Copyright

A mild robust generic protocol for the Suzuki reaction using an air stable catalyst

A mild but robust procedure has been developed as a first pass generic protocol for the Suzuki-Miyaura reaction. The protocol employs an air stable palladium pre-catalyst at low loading (1 mol %) in aqueous solvent mixtures at moderate temperature using potassium carbonate as base. Under these mild conditions, most aryl bromides will react with sterically and electronically demanding aryl boronic acids to give complete conversion to the product biphenyls in less than 1 h. Aryl chlorides are also fully converted in most cases either under identical conditions in 8-24 h, or in 2 h at elevated temperature. A further advantage of these mild conditions of moderate temperature, weak base and benign solvent is that sensitive functional groups and structural motifs are well tolerated. In addition, the lipophilic biphenyl products are readily isolated after a simple work-up procedure. These generic conditions are ideal for proof of transformation, and as the starting point for development and optimization of a specific process. The discovery and fine-tuning of this generic protocol will be presented, supported extensively by examples to illustrate its scope and utility.

Planar chiral P,O-compounds derived from ferrocenyl aryl ethers

The ortho-directed lithiation of FcOC6H4-4-tBu (1) [Fc = (η5-C5H4)(η5-C 5H5)Fe] with nBuLi/tmeda is reported (tmeda = tetramethylethylenediamine). In this reaction, multimetalation occurs to yield novel 1,2-functionalized P,O-derivatives that contain up to four phosphanyl moieties as determined by NMR spectroscopic studies and single-crystal X-ray diffraction analysis. Thus available planar chiral P,O-ferrocenes can successfully be applied in the palladium-catalyzed Suzuki coupling of diverse aryl halides and aryl boronic acids. The aforementioned systems allow the activation of carbon-chlorine bonds in an efficient way and tolerate catalyst loadings as low as 10 ppm. Noteworthy is their remarkable ability to economically generate hindered biaryls under mild reaction conditions. Planar chiral P,O-ferrocenes are excellent ligands in the palladium-mediated C-C coupling of aryl halides and aryl boronic acids. They allow either the conversion ofunreactive substrates or reactions to be performed at low catalyst levels. Moreover, multiply ortho-substituted biaryls are accessible under mild conditions.

Metal-free synthesis of sterically crowded biphenyls by direct Ar-H substitution in alkyl benzenes

(Chemical Equation Presented) Four's definitely a crowd: The chemoselective activation of Ar-H bonds in methylbenzenes by treatment with photogenerated phenyl cations allowed the synthesis of sterically crowded biphenyl compounds, including tetra-ortho-substituted biphenyls, by intermolecular cross-coupling (see scheme). This method is an appealing metal-free alternative to widely used transition-metal catalysis. TFE = 2,2,2-trifluoroethanol.

Synthesis of S-Substituted Benzils and Some Hindered Biphenyls

Three methylthio and/or methylsulfinyl substituted benzils (2, 6 and 7) have been synthesized on photo- or thermochemical routes, respectively.Photodecarboxylation of some new different substituted mesityl benzoates (1a-e) leads to hindered biphenyls (3a-e) accompanied sometimes by aldehyde (4a-c) and benzil formation (2) due to compatitive α-cleavage and subsequent stabilization processes of such generated free aroyl radicals.A short summary on constitutional conditions for intramolecular photoredox reactions of ortho functionalized aryl sulfinyl compounds is presented. - Keywords: Photodecarboxylations, α-Cleavages, Photoredox Reactions, Sulfoxides