82988-76-9

Upstream product

• 93731-78-3 benzenesulfonic acid, 4-methyl-, 2-[(2,4,6-trimethylphenyl)methylene]hydrazide 
• 487-68-3 mesytaldehyde 

Downstream Products

• 125154-84-9 Bis(trimethylsilyl)methylenephosphine 
• 28749-81-7 3,5-dimethylcyclobutabenzene 
• 17024-57-6 2,4,6,2',4',6'-hexamethyl-trans-stilbene 
• 76062-74-3 N,N'-Bis-[1-(2,4,6-trimethyl-phenyl)-meth-(E)-ylidene]-hydrazine 
• 487-68-3 mesytaldehyde 
• 1097638-93-1 (2,6-(2,6-(i)Pr₂-C₆H₃N=CMe)2C₅H₃N)Fe(NCC₆H₂(CH₃)3) 
• 1097638-94-2 (2,6-(2,6-(i)Pr₂-C₆H₃N=CMe)2C₅H₃N)Fe(NHCHC₆H₂(CH₃)3) 
• 125177-44-8 5-Mesityl-1,3-bis(trimethylsilyl)-1H-1,2,4-diazaphosphole 
• 125154-85-0 5-Mesityl-3-trimethylsilyl-1H-1,2,4-diazaphosphole 
• 4214-39-5 (Z)-1,2-dimesitylethene 

Relevant academic research and scientific papers

Direct Observation of Aryl Gold(I) Carbenes that Undergo Cyclopropanation, C?H Insertion, and Dimerization Reactions

Mesityl gold(I) carbenes lacking heteroatom stabilization or shielding ancillary ligands have been generated and spectroscopically characterized from chloro(mesityl)methylgold(I) carbenoids bearing JohnPhos-type ligands by chloride abstraction with GaCl3. The aryl carbenes react with PPh3 and alkenes to give stable phosphonium ylides and cyclopropanes, respectively. Oxidation with pyridine N-oxide and intermolecular C?H insertion to cyclohexane have also been observed. In the absence of nucleophiles, a bimolecular reaction, similar to that observed for other metal carbenes, leads to a symmetrical alkene.

Continuous Flow Synthesis and Purification of Aryldiazomethanes through Hydrazone Fragmentation

Electron-rich diazo compounds, such as aryldiazomethanes, are powerful reagents for the synthesis of complex structures, but the risks associated with their toxicity and instability often limit their use. Flow chemistry techniques make these issues avoidable, as the hazardous intermediate can be used as it is produced, avoiding accumulation and handling. Unfortunately, the produced stream is often contaminated with other reagents and by-products, making it incompatible with many applications, especially in catalysis. Herein is reported a metal-free continuous flow method for the production of aryldiazomethane solutions in a non-coordinating solvent from easily prepared, bench-stable sulfonylhydrazones. All by-products are removed by an in-line aqueous wash, leaving a clean, base-free diazo stream. Three successful sensitive metal-catalyzed transformations demonstrated the value of the method.

Catalytic asymmetric epoxidation of aldehydes. Optimization, mechanism, and discovery of stereoelectronic control involving a combination of anomeric and cieplak effects in sulfur ylide epoxidations with chiral 1,3-oxathianes

A range of 1,3-oxathianes based on camphorsulfonic acid have been prepared and tested in the catalytic asymmetric epoxidation of carbonyl compounds. It was found that the 1,3-oxathiane derived from acetaldehyde 5b gave the highest yield and enantioselectivity in the epoxidation process. The enantioselectivity was independent of the solvent and metal catalyst used (although yields were dependent on both). The optimum conditions were applied to a range of aldehydes, and good enantioselectivities and diastereoselectivities were observed. The origin of the enantioselectivity was probed, and in particular the role of the oxygen of the 1,3-oxathiane was investigated. Thus, the sulfur and carbon analogues of the camphorsulfonic acid based 1,3-oxathiane (derived from formaldehyde) were prepared (i.e., 1,3-dithiane and thiane analogues). With this series of analogues the steric effects are minimized so that the electronic effects can be investigated. The series of compounds was reacted in the catalytic cycle with benzaldehyde and gave stilbene oxides with 44% ee (sulfur analogue), 41% ee (1,3-oxathiane), and 20% ee (carbon analogue). Thus, it was concluded that the oxygen of the 1,3-oxathiane exerted a significant electronic effect in controlling the face selectivity of the ylide reactions. This electronic effect was a result of combined anomeric (higher with the sulfur analogue, not present with the carbon analogue) and Cieplak effects. A strong anomeric effect was observed in the X-ray structures of one of the 1,3-oxathianes, and an even greater one was observed in the corresponding sulfoxide (this was used as an electronic analogue of the ylide). The face selectivity of the ylide was believed to be complete in reactions with 5b. The minor enantiomer resulted from reaction of the minor conformer of the ylide, reacting again with high face selectivity. This was proven by using a more substituted diazo compound, which was expected to give much less of the minor conformer. Indeed, reaction with mesityldiazomethane gave the corresponding epoxide in essentially enantiomerically pure form.

Laser flash photolysis study of phenylcarbene, o-tolylcarbene and mesitylcarbene

Laser flash photolysis (LFP, XeCl, 308 nm, 20 ns) of phenyldiazomethane (PDM), o-tolydiazomethane (TDM) and mesitydiazomethane (MDM) produces phenylcarbene (PC), o-tolycarbene (TC) and mesitylcarbene (MSC), respectively. Transient spectra of PC and TC cou

THE SYNTHESIS OF ARYL DIAZOMETHANES

A convenient and rapid method for preparing aryldiazomethanes from the related tosylhydrazones employing phase transfer catalysis with hydrocarbon solvents in good to excellent yields has been developed.