120097-60-1

Upstream product

• 20734-18-3 diethyl 2-(hydroxymethylene)malonate 
• 87-13-8 diethyl 2-ethoxymethylenemalonate 
• 120097-56-5 diethyl α-difluoromethyl-α-phenylthiomalonate 
• 14064-08-5 diethyl 2-(phenylthio)malonate 
• 120097-58-7 2-Benzenesulfinyl-2-difluoromethyl-malonic acid diethyl ester 
• 72798-17-5 2-phenylsulfanylmethylene-malonic acid diethyl ester 

Downstream Products

• 130247-52-8 2-(4-Phenylsulfanyl-butylidene)-malonic acid diethyl ester 
• 130247-53-9 ethyl 2-ethoxycarbonyl-3-dimethyl(phenyl)silyl-2-propenoate 
• 13592-76-2 diethyl 2-(cyclohexylmethylene)malonate 

Relevant academic research and scientific papers

Free-Radical Carbo-Alkenylation of Olefins: Scope, Limitations and Mechanistic Insights

The three-component free-radical carbo-alkenylation of electron-rich olefins has been studied, varying the substitution pattern in the alkene, in the radical precursor and in the final acceptor. New vinylsulfones were also prepared and their reactivity investigated. The scope and limitations of the process was established, and the reaction mechanism clarified using selected dienes as radical clocks. It was thus recognised that the reversible addition onto the olefin of the released sulfonyl group is an important event, which should not be overlooked when using such multicomponent carbo-alkenylation reactions.

Preparation of functionalized Z-olefins using 1,1-dimetalloalkanes

1,1-Dimetalloalkanes obtained by the allylzincation of alkenylmagnesium compounds react smoothly with various functionalized alkylidenemalonates providing functionalized Z-olefins in good yields. If dimenthyl alkylidenemalonates are used, then excellent stereoselectivities are observed (92:8 to 100:0). An application to a short stereospecific synthesis of an insect pheromone [(Z)-7-dodecenyl acetate] is described (> 99.9% Z, 70% overall yield).

The Olefination of Functionalized Alkylidenemalonates by 1,1-Dimetalloalkanes: A New Chemo- and Stereoselective Preparation of Functionalized Olefins

The polyfunctional alkylidenemalonates 1, readily prepared by an addition-elimination reaction of FG-RCu(CN)ZnI to malonates of type 7, were found to undergo a highly chemoselective and stereoselective olefination reaction with 1,1-dimetalloalkanes of zinc and magnesium.An application to the stereospecific preparation of an insect pheromone 8 is reported.