60386-54-1

Upstream product

• 61771-75-3 ethyl 1-allyl-2-oxocyclohexanecarboxylate 
• 108-94-1 cyclohexanone 
• 123-38-6 propionaldehyde 
• 1655-07-8 ethyl 2-oxocyclohexane carboxylate 
• 92695-29-9 2-(prop-1-en-1-yl)cyclohexan-1-one 
• 94-66-6 2-allylcyclohexan-1-one 

Downstream Products

• 94-65-5 2-(n-propyl)cyclohexanone 
• 85123-20-2 4-ethyl-3-phenyl-1-oxa-2-aza-spiro[4.5]dec-2-en-6-one 
• 94821-68-8 4-ethyl-3-phenyl-1-oxa-2-aza-spiro[4.5]dec-2-en-6-one oxime 
• 36302-45-1 (R)-2-propylcyclohexanone 
• 67113-13-7 (S)-(+)-2-propylcyclohexan-1-one 
• 227081-31-4 (S)-2-Hydroxy-2-((R)-1-hydroxy-propyl)-cyclohexanone 
• 55229-19-1 3-ethyl-5,6,7,7a-tetrahydrobenzofuran-2(4H)-one 

Relevant academic research and scientific papers

Stereoselective alkene isomerization over one position

Although controlling both the position of the double bond and E:Z selectivity in alkene isomerization is difficult, 1 is a very efficient catalyst for selective mono-isomerization of a variety of multifunctional alkenes to afford >99.5% E-products. Many reactions are complete within 10 min at room temperature. Even sensitive enols and enamides susceptible to further reaction can be generated. Catalyst loadings in the 0.01-0.1 mol% range can be employed. E-to-Z isomerization of the product from diallyl ether was only -6 times as fast as its formation, showing the extremely high kinetic selectivity of 1.

Highly active and selective platinum(II)-catalyzed isomerization of allylbenzenes: Efficient access to (E)-anethole and other fragrances via unusual agostic intermediates

Terminal alkene isomerization reactions can be efficiently catalyzed by PtII complexes bearing a chelating diphosphine and an alkyl or, better, aryl moiety under mild experimental conditions. In particular diphosphines, such as dppb, characterized by a large bite angle in conjunction with a pentafiuorophenyl residue coordinated to Pt enable quantitative conversion of the reagent into internal, alkenes within few hours at 50 °C in CHCl3 as solvent. E/Z selectivity can be as high as 98:2 for allylbenzene, and the catalytic system can be fruitfully applied to the preparation of E fragrances derived by isomerization of substituted, allylbenzene derivatives. The selectivity increases during the progress of the reaction because of a subsequent catalytic step where the Z alkene coordinates to the Pt and is converted into the E isomer. NMR investigation on the catalyst showed formation of agostic Pt...H intermediate species derived by insertion of the substrate into the Pt-aryl bond followed by β-hydride elimination. Formation of such agostic species is promoted by the steric hindrance imparted by the diphosphine characterized by a large bite angle. Kinetic studies and DFT calculations on the possible agostic intermediates shed light on their structure and enable the formulation of a possible catalytic mechanism.

An efficient procedure for the preparation of (E)-α-alkylidenecycloalkanones mediated by a CeCl3·7H2O-NaI system. Novel methodology for the synthesis of (S)-(-)-pulegone

2-Alkylidenecycloalkanones are powerful synthons used as the key intermediates in many important syntheses. Because of their potential, a general method of preparation from readily available starting materials, under very mild conditions, was considered to be worthwhile. Cerium(III) chloride heptahydrate in combination with sodium iodide in refluxing acetonitrile promotes a regio- and stereoselective β-elimination reaction to (E)-2-alkylidenecycloalkanones in 2-(1-hydroxyalkyl)cycloalkanones. The synthetic value of the present procedure is demonstrated by the synthesis of monoterpene (S)-(-)-pulegone (8) in its optically active form.