14618-89-4

Upstream product

• 3350-78-5 3,3-Dimethylacryloyl chloride 
• 108-88-3 toluene 
• 4294-57-9 para-methylphenylmagnesium bromide 
• 920957-35-3 3-hydroxy-3-methyl-1-(4-methylphenyl)butane-1-one 
• 104-87-0 4-methyl-benzaldehyde 
• 41801-78-9 1-(4-methylphenyl)-3-methylbut-3-en-1-ol 
• 820-71-3 methallyl acetate 
• 201230-82-2 carbon monoxide 
• 5720-05-8 4-methylphenylboronic acid 
• 50390-51-7 4'-methylisobutyrophenone 
• 1355253-91-6 C₁₅H₂₄OSi 
• 7163-50-0 (4-methylphenyl)(oxo)acetic acid 
• 1360924-11-3 allyl 2-oxo-2-(p-tolyl)acetate 
• 1360924-17-9 2-methylallyl 2-oxo-2-phenylacetate 

Downstream Products

• 681215-86-1 3,3,-dimethyl-1-(p-tolyl)butan-1-one 
• 96633-37-3 1-phenyl-2,3,3-trimethyl-5-p-tolyl-1,5-pentanedione 
• 1168156-47-5 2-ethoxy-4,4-dimethyl-6-p-tolyl-3,4-dihydro-2H-pyran 
• 92236-76-5 (3,3-Dimethyl-aziridin-2-yl)-p-tolyl-methanol 

Relevant academic research and scientific papers

Asymmetric Alkoxy- and Hydroxy-Carbonylations of Functionalized Alkenes Assisted by β-Carbonyl Groups

As a fundamental type of carbonylation reaction, the alkoxy- and hydroxy-carbonylation of unsaturated hydrocarbons constitutes one of the most important industrial applications of homogeneous catalysis. However, owing to the difficulties in controlling multi-selectivities for asymmetric hydrocarbonylation of alkenes, this reaction is typically limited to vinylarenes and analogues. In this work, a highly efficient asymmetric alkoxy- and hydroxy-carbonylation of β-carbonyl functionalized alkenes was developed, providing practical and easy access to various densely functionalized chiral molecules with high optical purity from broadly available alkenes, CO, and nucleophiles (>90 examples, 84–99 % ee). This protocol features mild reaction conditions and a broad substrate scope, and the products can be readily transformed into a diverse array of chiral heterocycles. Control experiments revealed the key role of the β-carbonyl group in determining the enantioselectivity and promoting the activity, which facilitates chiral induction by coordination to the transition metal as rationalized by DFT calculations. The strategy of utilizing an innate functional group as the directing group on the alkene substrate might find further applications in catalytic asymmetric hydrocarbonylation reactions.

Visible Light Mediated Photocatalytic N-Radical Cascade Reactivity of O,δ-Unsaturated N-Arylsulfonylhydrazones: A General Approach to Structurally Diverse Tetrahydropyridazines

Tetrahydropyridazines are of particular interest for their versatility as intermediates in organic synthesis and display pharmacological activity in several domains. Here, we describe the photocatalytic synthesis of different tetrahydropyridazines starting from O,δ-unsaturated N-arylsulfonylhydrazones. Simple structural changes of substrates result into three different pathways beginning from a common N-hydrazonyl radical, which evolves through a domino carboamination/dearomatization, a HAT process, or a photoinduced radical Smiles rearrangement to afford diverse tetrahydropyridazines. All reactions are carried out in very mild conditions, and the quite inexpensive [Ru(bpy)3]Cl2 is used as the catalyst. Preliminary mechanism studies are presented, among them luminescence and electrochemical characterization of the involved species. Computational studies allow to rationalize the mechanism in accord with the experimental findings.

Carbonylative coupling of allylic acetates with aryl boronic acids

The first allylic carbonylation reaction of allylic acetates with aryl boronic acids under carbon monoxide has been developed. Using Pd-PCy3 as a catalyst, a wide spectrum of allylic acetates was carbonylated in the presence of various aryl boronic acids, affording α,β-unsaturated aryl ketones in good to excellent yields. Preliminary studies indicate that carbon monoxide always inserts at the least substituted terminal allylic carbon and the resulting β,γ-unsaturated aryl ketones generally isomerise to the ketones obtained.

Synthesis of α-indanones via intramolecular direct arylation with cyclopropanol-derived homoenolates

A palladium-catalysed, tandem cyclopropanol rearrangement and direct arylation approach for the synthesis of 1-indanones is reported. The reaction is generally high yielding, uses oxygen as the terminal oxidant and tolerates a range of functional groups on the aryl ring.

Synthesis of α,β-unsaturated ketones by Pd-catalyzed decarboxylative allylation of α-oxocarboxylates

A palladium/p-tolylphosphine system has been developed that catalyzes the extrusion of carbon dioxide from α-oxocarboxylic acid allyl esters, leading to α,β-unsaturated ketones (see scheme). The palladium complex activates the substrate and mediates the carbon-carbon bond formation to give allyl ketones, and subsequent double bond shift to the α,β position. The actual decarboxylation step with formation of the acyl nucleophile is promoted by phosphine.

Experimental and theoretical studies of a one-flask synthesis of 3H-1-benzazepines from 2-haloanilines and α,β-unsaturated ketones

3H-1-Benzazepines are prepared in one step from the reaction of 2-fluoro- or 2-chloroaniline and several aryl vinyl ketones. Enones 9a-c gave benzazepines 11a-c as expected, showing that alkyl substitution at C4 and C5 in the benzazepines is possible. However, enone 9d underwent decomposition due to conjugate addition of the 2-fluoroaniline, while enone 10 gave unsaturated imine 12 as the only product able to be isolated. The failure of unsaturated imine 12 to undergo cyclization may indicate that placement of an alkyl group at C3 of the benzazepines may not be possible. Isolation of by-products buttressed by a computational study verifies a postulated, multi-step process for benzazepine formation: a [1,5] sigmatropic shift in fluoroimine 3, addition elimination to give carbocation 15, formation of the unstable 5H-1-benzazepine 7, and acid-catalyzed isomerization to give the stable 3H-1-benzazepine 2. The calculations also indicate why unsaturated imine 12 fails to cyclize. NMR spectroscopic experiments show that the 3H-benzazepines undergo fast conformational exchange on the NMR time scale at room temperature except when there is an alkyl substituent at C5.

Adrenoceptor Blocking Agents: Part III - Synthesis of 2-(&α-Hydroxyarylmethyl)-3,3-dimethylaziridines as Selective &β2-Adrenoceptor Antagonists

threo-2-(α-Hydroxy-4-substituted benzyl)-3,3-dimethylaziridines (20-22) and threo-N-substituted-2-(α-hydroxybenzyl)-3,3-dimethylaziridines (18 and 23) have been synthesized and evaluated for their β-adrenoceptor blocking activity.Compounds 20-22 are more