428442-20-0

Upstream product

• 696-63-9 4-Methoxybenzenethiol 
• 1663-67-8 malonoyl dichloride 
• 51932-41-3 malonic acid monochloride 

Downstream Products

• 63668-66-6 S-(p-Methoxyphenyl)-3-oxobutanthioat 
• 60787-31-7 S-(4-methoxyphenyl) ethanethioate 
• 1352957-49-3 C₁₈H₁₉NO₄S 
• 94252-16-1 C₁₅H₁₅NO₃S 
• 1352957-51-7 C₁₇H₁₆FNO₄S 
• 1352957-53-9 C₁₇H₁₆BrNO₄S 
• 1352957-58-4 C₁₃H₁₉NO₃S 
• 1352957-56-2 C₁₅H₂₁NO₄S 

Relevant academic research and scientific papers

Synthesis of Monothiomalonates – Versatile Thioester Enolate Equivalents for C–C Bond Formations

Monothiomalonates (MTMs) are surrogates of thioester enolates that allow for stereoselective C–C bond formations under mild conditions and thereby afford access to synthetically versatile thioester derivatives. Here we present a straightforward synthetic route to MTMs that proceeds through nucleophilic ring-opening of Meldrum's acid derivatives followed by O-alkylation of the resulting malonic acid half thioesters with alkyl triflates or acetimidates as electrophiles. The method affords MTMs in overall yields of 34?–?92% and allows for variations of the oxo- and thioester moieties as well as the substituent at the C(α) position.

Gaining Insight Into Reactivity Differences Between Malonic Acid Half Thioesters (MAHT) and Malonic Acid Half Oxyesters (MAHO)

An efficient two-step synthesis of structurally and functionally diverse thiophenol- and (cyclo)alkyl-derived malonic acid half thioesters (MAHTs) and phenol-derived malonic acid half oxyesters (MAHOs) has been achieved using cheap, readily available and easily handled starting materials. The synthesis of the MAHTs and MAHOs (the majority of which have not been previously reported) is readily scalable to afford gram quantities of product. In a hydrogen→deuterium exchange, an interesting stereoelectronic effect was observed when different aryl groups were incorporated. Significant changes in the rates of hydrogen→deuterium exchange and levels of isotope incorporation were observed. By way of example, using [2H]methanol and 4-bromophenol-derived MAHO afforded only 14 % [2H]-incorporation (9 min, k=31) whereas the corresponding 4-bromothiophenol-derived MAHT afforded 97 % [2H]-incorporation (9 min, k=208). In a benchmark procedure and comprehensive DFT study, 54 ester and thioester configurations and conformations were characterized. In the MAHT series, a sulfur-containing molecular orbital provides a path for increased delocalisation of electron density into the enol that is unavailable in MAHOs. This facilitates keto–enol tautomerisation and consequently enhances the rate and percentage of hydrogen→deuterium exchange.

Organocatalytic enantioselective decarboxylative aldol reaction of malonic acid half thioesters with aldehydes

Copycat: A highly enantioselective biomimetic aldol reaction of malonic acid half thioesters with a variety of aldehydes affords optically active β-hydroxy thioesters by employing the cinchona-derived sulfonamide organocatalyst 1. The synthetic utility of this protocol was demonstrated by performing formal syntheses of the antidepressants (R)-fluoxetine, (R)-tomoxetine, (-)-paroxetine, and (R)-duloxetine. Copyright

Malonic acid half oxyesters and thioesters: Solvent-free synthesis and DFT analysis of their enols

A much improved synthetic route to malonic acid half thioesters (MAHTs) and oxyesters (MAHOs), the easy incorporation of deuterium labeling expecially in MAHTs, and an unexpectedly large difference in enolization chemistry between MAHTs and MAHOs are repo

Mg2+-imidazole-catalyzed self-condensation of malonyl thioesters: Getting tuned for biomimetic polyketide synthesis?

We report that a subtle balance of carbanion reactivity, leaving group activation, and pKa of the catalyst is required for efficient self-condensation of thiomalonates to thioacetoacetates in up to 71% yield under "biomimetic" conditions originally proposed by Kobuke and Yoshida (Tetrahedron Lett. 1978, 19, 367).