35293-95-9

Upstream product

• 2181-42-2 trimethylsulphonium iodide 
• 5292-53-5 diethyl benzalmalonate 
• 74-88-4 methyl iodide 
• 536-74-3 phenylacetylene 
• 609-08-5 Diethyl methylmalonate 

Downstream Products

• 35205-58-4 ethyl 2-methyl-2-carboethoxy-3-phenylbutyrate 

Relevant academic research and scientific papers

Indium-catalyzed 2-alkenylation of 1,3-dicarbonyl compounds with unactivated alkynes

1,3-Dicarbonyl compounds add to unactivated alkynes in the presence of a catalytic amount of indium(lll) trifluoromethanesulfonate in high to excellent yield to give 2-alkenylated 1,3-dicarbonyl compounds with exclusive regioselectivity as to the position of C-C bond formation on the acetylene moiety. In most of the cases, the reaction requires less than 1-mol % loading of the catalyst and does not require solvent. The reaction tolerates a wide variety of functional groups including ester, ether, allylic halide, furan, thiophene, and protected amine. Experimental and theoretical studies suggested that the reaction proceeds via a concerted carbometalation reaction of an indium(lll) enolate with the acetylene, where indium - acetylene interaction is important.

Indium (III) mediated Markovnikov addition of malonates and β-ketoesters to terminal alkynes and the formation of Knoevenagel condensation products

The indium(III) triflate mediated addition of active methylene compounds to terminal alkynes has been expanded to use malonates and low boiling terminal alkynes to form the Markovnikov addition products. Indium(III) chloride and indium(III) bromide were also found to be efficient catalysts. Knoevenagel condensation products were isolated when reactions involved a simple malonate or β-ketoester.

The unprecedented reaction of dimethylsulfonium methylide with Michael acceptors: Synthesis of 1-substituted vinyl silanes and styrenes

Rather than the usual cyclopropanation, conditions for an unprecedented elimination reaction from the adduct of dimethylsulfonium methylide and various Michael acceptors have been established leading to functionalized 1-substituted alkenes. In silyl substituted substrates (2a and 2h), where a facile Peterson-type olefination is possible from the adduct; elimination took place instead to give functionalized 1 -substituted vinyl silanes. Aryl substituted Michael acceptors (2b-e, 2g and 2i-k) also underwent a similar kind of olefination to give 1-substituted styrene derivatives with moderate yields along with a side product, which arose by nucleophilic demethylation from the adduct of dimethylsulfonium methylide and arylidene malonates. Hammett studies revealed that selectivity for olefination vs. demethylation increases as the aryl substituent becomes more electron deficient. Alkylidene malonates (2f and 2l) with a β-alkyl substituent did not favour the olefination process. Sequential addition of Michael acceptors and alkyl halides to a mixture of dimethylsulfonium methylide and sodium dimsylate provided olefination followed by alkylation on the active methine group. A mechanistic pathway has been formulated from the studies of a few sulfonium methylides. The Royal Society of Chemistry 2005.

A novel reaction of dimethylsulfonium methylide with Michael acceptors: Application to the synthesis of difficulty accessible vinyl silanes and styrenes

Rather than the usual cyclopropanation and Peterson-type olefination, conditions for a novel elimination reaction from the adduct of dimethylsulfonium methylide and 2-silylalk-ylidene/arylidene malonate/cyanoacetate/phosphonoacetate leading to geminally s