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Upstream product

• 101-77-9 4,4'-diamino diphenyl methane 
• 76-09-5 2,3-dimethyl-2,3-butane diol 
• 61676-62-8 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 
• 1941-86-2 bis(4-bromophenyl)methane 
• 73183-34-3 bis(pinacol)diborane 
• 106-37-6 1.4-dibromobenzene 
• 1122-91-4 4-bromo-benzaldehyde 
• 29334-18-7 bis-(4-bromophenyl)methanol 
• 333-27-7 methyl trifluoromethanesulfonate 
• 101-81-5 Diphenylmethane 
• 22092-92-8 diisopropopylaminoborane 
• 53091-46-6 4,4'-diphenylmethanebisdiazonium ditetrafluoroborate 

Relevant academic research and scientific papers

Arene borylation through C–H activation using Cu3(BTC)2 as heterogeneous catalyst

C–H borylation by diborane is an important process to access organoboron compounds. Noble metals, including Ir and Rh-based complexes either in the form of homogeneous or heterogeneous catalysts, have been reported to promote arene C–H borylation. Recently, metal organic frameworks (MOFs) having Ir and Co as active sites have been used as catalysts, but they require co-catalysts. In the present study, commercially available Cu3(BTC)2 (BTC: 1,3,5-benzenetricarboxylate) MOF is reported as an effective catalyst to promote borylation of arenes through C–H activation employing bis(pinacolato)diboron (1) as reagent leading to benzylic and aromatic borylation products. Interestingly, other related MOFs like MIL-101(Cr) and Al(OH)(BDC) (BDC: 1,4-benzenedicarboxylate) do not exhibit catalytic activity under identical conditions. Mechanistic studies using in-situ IR spectroscopy reveal that Cu ions play a crucial role in activating the arene and B–B bond in 1.

Visible Light-Induced Borylation of C-O, C-N, and C-X Bonds

Boronic acids are centrally important functional motifs and synthetic precursors. Visible light-induced borylation may provide access to structurally diverse boronates, but a broadly efficient photocatalytic borylation method that can effect borylation of a wide range of substrates, including strong C-O bonds, remains elusive. Herein, we report a general, metal-free visible light-induced photocatalytic borylation platform that enables borylation of electron-rich derivatives of phenols and anilines, chloroarenes, as well as other haloarenes. The reaction exhibits excellent functional group tolerance, as demonstrated by the borylation of a range of structurally complex substrates. Remarkably, the reaction is catalyzed by phenothiazine, a simple organic photocatalyst with MW 200 that mediates the previously unachievable visible light-induced single electron reduction of phenol derivatives with reduction potentials as negative as approximately - 3 V versus SCE by a proton-coupled electron transfer mechanism. Mechanistic studies point to the crucial role of the photocatalyst-base interaction.

Through-space π-delocalization in a conjugated macrocycle consisting of [2.2]paracyclophane

Herein, we report the synthesis and characterization of a [2.2]paracyclophane-containing macrocycle (PCMC) as a new through-space conjugated macrocycle using only benzene groups as the skeleton. For comparison, a diphenylmethane-containing nanohoop macrocycle (DCMC) with a non-conjugated linker was also synthesized. Their structures were confirmed by NMR and HR-MS, and their photophysical properties were studied by UV-vis and fluorescence spectroscopies combined with theoretical calculations. The strain energy of PCMC was estimated to be as high as 72.58 kcal mol-1.

Methane-perylene diimide-based small molecule acceptors for high efficiency non-fullerene organic solar cells

We report perylene diimide (PDI) small molecules based on diphenylmethane, triphenylmethane, and tetraphenylmethane cores, named PM-PDI2, PM-PDI3 and PM-PDI4, respectively. The OSC performances of PM-PDI3 and PM-PDI4 are comparable. The PM-PDI3 based device with PDBT-T1 as the donor achieved a highest power conversion efficiency (PCE) of 7.58% along with a high open-circuit voltage (VOC) of 0.98 V, a short-circuit current density (JSC) of 11.02 mA cm-2 and a high fill factor (FF) of 69.9%, a 1.32 times boost in PCE with respect to the PM-PDI2 based control device (3.26%). The high photovoltaic performance of the PM-PDI3 based device can be attributed to its relatively high-lying LUMO level, complementary absorption spectra with the polymer donor material PDBT-T1, relatively favorable morphology and improved exciton dissociation and charge collection efficiency. A PCE of 7.58% is among the highest efficiency of phenyl-methane as core based non-fullerene organic solar cells. Overall, this work provides a new approach to enhance the performance of non-fullerene acceptors.

Nickel-Catalyzed Borylation of Aryl- and Benzyltrimethylammonium Salts via C-N Bond Cleavage

By developing a mild Ni-catalyzed system, a method for direct borylation of sp2 and sp3 C-N bonds has been established. The key to this hightly efficient C-N bond borylative cleavage depends on the appropriate choice of the nickel catalyst Ni(COD)2, ICy·HCl as a ligand, and the use of 2-ethoxyethanol as the cosolvent. This transformation shows good functional group compatibility and can serve as a powerful synthetic tool for gram-scale synthesis and late-stage C-N borylation of complex compounds.

New process for preparing arylboranes by arylation of organoboron compounds

The present invention relates to a new process for the preparation of an arylborane compound, by arylation of a B-H bond, which comprises a step (1) of contacting an arenediazonium salt or a heteroarenediazonium salt with an organoboron compound containing at least one B-H bond, in a reaction medium containing a solvent, in the absence of base, in the absence or in the presence of an activating agent, for the preparation of an arylborane compound, and a possible step (2) of recovery and purification of said arylborane compound obtained at the step (1), said arylborane being in particular an aminoarylborane, and a possible step (3) of refunctionalisation of said arylborane obtained at step (1) or (2) for the preparation of aryl boronic derivatives or arylborates.

Borylation using group IV metallocene under mild conditions

A borylation reaction of aromatic diazonium salts has been optimized using titanocene and zirconocene derivatives as catalysts. The reaction employs diisopropylaminoborane as a borylating agent and proceeds smoothly at room temperature to provide arylboronates after methanolysis and transesterification with pinacol. The reaction mechanism has been found to proceed via a radical pathway.

NEW PROCESS FOR PREPARING ARYLBORANES BY ARYLATION OF ORGANOBORON COMPOUNDS

The present invention relates to a new process for the preparation of an arylborane compound, by arylation of a B-H bond, which comprises a step (1) of contacting an arenediazonium salt or a heteroarenediazonium salt with an organoboron compound containing at least one B-H bond, in a reaction medium containing a solvent, in the absence of base, in the absence or in the presence of an activating agent, for the preparation of an arylborane compound, and a possible step (2) of recovery and purification of said arylborane compound obtained at the step (1), said arylborane being in particular an aminoarylborane, and a possible step (3) of refunctionalisation of said arylborane obtained at step (1) or (2) for the preparation of aryl boronic derivatives or arylborates.

The effects of cyclic conjugation and bending on the optoelectronic properties of paraphenylenes

Cycloparaphenylenes (CPPs) have optoelectronic properties that are unique when compared to their acyclic oligoparaphenylene counterparts. The synthesis and characterization of two bent heptaphenyl-containing macrocycles has been achieved in order to probe

Iron-catalysed borylation of arenediazonium salts to give access to arylboron derivatives via aryl(amino)boranes at room temperature

Complementary to previously described Miyaura borylation methods, a new access to boron derivatives via aryl(amino)boranes is described. Direct coupling between aryldiazonium salts and diisopropylaminoborane is catalysed by 0.1% ferrocene leading to the formation of a carbon-boron bond. The obtained aryl(amino)boranes could eventually then be transformed into boronic acids, boronates or borates. Copyright