24254-66-8

Upstream product

• 186581-53-3 diazomethane 
• 359713-41-0 1,1-dicyano-2-(4'-methylphenyl)propane 
• 96-32-2 bromoacetic acid methyl ester 
• 122-00-9 para-methylacetophenone 
• 623-43-8 crotonic acid methyl ester 
• 4294-57-9 para-methylphenylmagnesium bromide 
• 5720-05-8 4-methylphenylboronic acid 
• 20754-20-5 3-p-tolyl-acrylic acid methyl ester 
• 917-54-4 methyllithium 
• 67-56-1 methanol 
• 50-00-0 formaldehyd 
• 1195-32-0 1-methyl-4-isopropenylbenzene 
• 201230-82-2 carbon monoxide 
• 3111-61-3 2-[1-(4-methylphenyl)ethylidene]malononitrile 

Relevant academic research and scientific papers

Synthetic studies toward anisatin: a formal synthesis of (+/-)-8-deoxyanisatin.

[figure: see text] An efficient strategy to construct the congested C-7a quaternary chiral center of anisatin was developed, by way of an Eschenmoser-Claisen rearrangement. Conversion of the resultant amide to Kende's epsilon-lactone intermediate 3 in four steps completed a concise formal synthesis of (+/-)-8-deoxyanisatin (2).

Development of efficient palladium catalysts for alkoxycarbonylation of alkenes

Herein, we report a general and efficient Pd-catalysed alkoxycarbonylation of sterically hindered and demanding olefins including a variety of tri-, tetra-substituted and 1,1-disubstituted alkenes. In the presence of 1,3-bis(tert-butyl(pyridin-2-yl)phosphanyl)propane L3 or 1,4-bis(tert-butyl(pyridin-2-yl)phosphanyl)butane L4 the desired esters are obtained in good yields and selectivities. Similar transformation is obtained using tertiary ether as showcased in the carbonylation of MTBE to the corresponding linear ester in high yield and selectivity.

Regioselective Pd-Catalyzed Methoxycarbonylation of Alkenes Using both Paraformaldehyde and Methanol as CO Surrogates

In recent years, considerable effort has focused on the development of novel carbonylative transformations using CO surrogates. Consequently, toxic CO gas can be replaced by more convenient inorganic or organic carbonyl compounds. Herein, the first regioselective methoxycarbonylation of alkenes with paraformaldehyde and methanol as CO substitutes is reported. This new procedure is applicable to a series of alkenes in the presence of a palladium catalyst under relatively mild conditions and is highly atom efficient.

Synthesis of (R)-ar-turmerone and its conversion to (R)-ar-himachalene, a pheromone component of the flea beetle: (R)-ar-himachalene is dextrorotatory in hexane, while levorotatory in chloroform

(R)-ar-Turmerone was synthesized from (4-methylphenyl)acetic acid by employing Evans asymmetric alkylation as the key step. (R)-ar-Turmerone was converted to (R)-ar-himachalene, which was dextrorotatory in hexane while levorotatory in chloroform. Enantiomerically impure (75% ee) (R)-3-(4-methylphenyl)butanoic acid crystallized more readily than the enantiomerically pure one.

Rhodium-catalyzed 1,4-addition of arylboronic acids to α,β-unsaturated carbonyl compounds: Large accelerating effects of bases and ligands

The effects of ligands and bases in the rhodium(I)-catalyzed 1,4-addition of arylboronic acids to α,β-unsaturated carbonyl compounds were reinvestigated to carry out the reaction under mild conditions. Rhodium(I) complexes possessing a 1,5-cyclooctadiene (cod) and a hydroxo ligand such as [RhOH(cod)]2 exhibited excellent catalyst activities compared to those of the corresponding rhodium-acac or -chloro complexes and their phosphine derivatives. The reaction was further accelerated in the presence of KOH, thus allowing the 1,4-addition even at 0 °C. A cationic rhodium-(I)-(R)-binap complex, [Rh(R-binap)(nbd)]BF4, catalyzed the reaction at 25-50 °C in the presence of Et3N with high enantioselectivities of up to 99% ee for α,β-unsaturated ketones, 92% for aldehydes, 94% for esters, and 92% for amides.

A conjugate addition of arylboronic acids to α,β-unsaturated carbonyl compounds catalyzed by 2β-CD-[Rh(OH)(cod)]2 or [RhCl(cod)]2 in a single aqueous medium

The rhodium-catalyzed conjugate addition of tolylboronic acid to α,β-unsaturated ketones, esters or amides was carried out in water. [RhCl(cod)]2 and 2β-cyclodextrin-[Rh(OH)(cod)]2 complexes were found to catalyze the reaction efficiently in a single aqueous medium.