193486-54-3

Upstream product

• 6327-79-3 1-(4-methoxyphenyl)-3-phenylpropane-1,3-dione 
• 74-88-4 methyl iodide 
• 104-92-7 1-bromo-4-methoxy-benzene 
• 201230-82-2 carbon monoxide 
• 93-55-0 1-phenyl-propan-1-one 
• 696-62-8 para-iodoanisole 
• 614-45-9 tert-Butyl peroxybenzoate 
• 959-33-1 3-(4-methoxyphenyl)-1-phenylprop-2-en-1-one 

Downstream Products

• 71591-81-6 2,2-dimethyl-1-(4'-methoxyphenyl)-3-phenyl-1,3-propanedione 
• 100-09-4 4-methoxybenzoic acid 
• 65-85-0 benzoic acid 

Relevant academic research and scientific papers

Copper-catalyzed methylation of 1,3-diketones with tert-butyl peroxybenzoate

Copper-catalyzed radical methylation of 1,3-diketones with tert-butyl peroxybenzoate in air is described, providing a general pathway to α-methyl 1,3-diketones in moderate to good yields. This protocol has been scaled up to 50?g, and one of the synthesized products can be used in the synthesis of medicine, Rosuvastatin.

Pd-catalyzed carbonylative α-arylation of aryl bromides: Scope and mechanistic studies

Reaction conditions for the three-component synthesis of aryl 1,3-diketones are reported applying the palladium-catalyzed carbonylative α-arylation of ketones with aryl bromides. The optimal conditions were found by using a catalytic system derived from [Pd(dba)2] (dba=dibenzylideneacetone) as the palladium source and 1,3-bis(diphenylphosphino)propane (DPPP) as the bidentate ligand. These transformations were run in the two-chamber reactor, COware, applying only 1.5 equivalents of carbon monoxide generated from the CO-releasing compound, 9-methylfluorene-9-carbonyl chloride (COgen). The methodology proved adaptable to a wide variety of aryl and heteroaryl bromides leading to a diverse range of aryl 1,3-diketones. A mechanistic investigation of this transformation relying on 31P and 13C NMR spectroscopy was undertaken to determine the possible catalytic pathway. Our results revealed that the combination of [Pd(dba)2] and DPPP was only reactive towards 4-bromoanisole in the presence of the sodium enolate of propiophenone suggesting that a [Pd(dppp)(enolate)] anion was initially generated before the oxidative-addition step. Subsequent CO insertion into an [Pd(Ar)(dppp)(enolate)] species provided the 1,3-diketone. These results indicate that a catalytic cycle, different from the classical carbonylation mechanism proposed by Heck, is operating. To investigate the effect of the dba ligand, the Pd0 precursor, [Pd(η3-1-PhC 3H4)(η5-C5H5)], was examined. In the presence of DPPP, and in contrast to [Pd(dba)2], its oxidative addition with 4-bromoanisole occurred smoothly providing the [PdBr(Ar)(dppp)] complex. After treatment with CO, the acyl complex [Pd(CO)Br(Ar)(dppp)] was generated, however, its treatment with the sodium enolate led exclusively to the acylated enol in high yield. Nevertheless, the carbonylative α-arylation of 4-bromoanisole with either catalytic or stoichiometric [Pd(η3-1-PhC3H4) (η5-C5H5)] over a short reaction time, led to the 1,3-diketone product. Because none of the acylated enol was detected, this implied that a similar mechanistic pathway is operating as that observed for the same transformation with [Pd(dba)2] as the Pd source. CO-operation is the key! The first palladium-catalyzed carbonylative α-arylation of aryl bromides is described. A wide array of different aryl 1,3-diketones can be isolated in good-to-excellent yields using only stoichiometric amounts of CO (see scheme). A mechanistic study is presented that suggests the need for enolate coordination prior to oxidative addition when [Pd(dba)2] is employed as the precatalyst. Copyright

Palladium-catalyzed carbonylative α-arylation for accessing 1,3-diketones

With a hint of CO: The first Pd-catalyzed carbonylative α-arylations of simple ketones with carbon monoxide is presented for the direct synthesis of 1,3-diketones (see scheme). The method uses only stoichiometric amounts of CO, and hence allows for the si

Clemmensen reduction. XII The synthesis and acidolysis of some diaryl-substituted cyclopropane-1,2-diols. The possible involvement of a cyclopropyl cation

The generation of a number of 1,2-diarylcyclopropane-1,2-diols is reported. Reaction of these in situ with acid gives, primarily, an α,β-unsaturated ketone in which the aryl substituent attached to the double bond is that which is best able to stabilize a benzylic cation. It is proposed that the reaction proceeds by O-protonation of the cyclopropane- 1,2-diol, followed by loss of water and opening of the resulting cyclopropyl cation and final deprotonation. Such initial O-protonation contrasts with the C-protonation normally observed in the acidolysis of cyclopropanols and other dialkyl- and alkylaryl-cyclopropane-1,2-diols.