61668-14-2

Upstream product

• 141-82-2 malonic acid 
• 100-53-8 phenylmethanethiol 
• 51932-41-3 malonic acid monochloride 
• 1663-67-8 malonoyl dichloride 
• 32362-99-5 benzylthioacetate 
• 124-38-9 carbon dioxide 

Downstream Products

• 32362-99-5 benzylthioacetate 
• 54565-04-7 Acetylthioessigsaeure-S-benzylester 
• 941569-56-8 S-benzyl 3-hydroxy-4-phenylbutanethioate 
• 504414-72-6 3-methoxymethoxy-5-phenyl-pentanethioic acid S-benzyl ester 
• 1259130-31-8 (S)-S-benzyl 3-(3-(cyclopentyloxy)-4-methoxyphenyl)-4-nitrobutanethioate 
• 1259130-15-8 (R)-S-benzyl 3-(furan-2-yl)-4-nitrobutanethioate 
• 1259130-16-9 (R)-S-benzyl 4-nitro-3-(thiophen-2-yl)butanethioate 
• 1259130-13-6 (S)-S-benzyl 4-nitro-3-p-tolylbutanethioate 
• 957770-88-6 (R)-S-benzyl 4-nitro-3-phenylbutanethioate 
• 1259314-72-1 (S)-S-benzyl 4-nitro-3-phenylbutanethioate 

Relevant academic research and scientific papers

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

Expanding the utility of Bronsted base catalysis: Biomimetic enantioselective decarboxylative reactions

As a result of the low reactivity of simple esters, the use of them as nucleophiles in direct asymmetric transformations is a long-standing challenge in synthetic organic chemistry. Nature approaches this difficulty through a decarboxylative mechanism, which is used for polyketide synthesis. Inspired by nature, we report guanidine-catalyzed biomimetic decarboxylative C-C and C-N bond-formation reactions. These highly enantioselective decarboxylative Mannich and amination reactions utilized malonic acid half thioesters as simple ester surrogates. It is proposed that nucleophilic addition precedes decarboxylation in the mechanism, which has been investigated in detail through the identification of intermediates by using electrospray ionization (ESI) mass-spectrometric analysis and DFT calculations. Copyright

Bioinspired metal-catalysed Doebner-Knoevenagel condensations between malonic acid half thioesters and aldehydes

Inspired by polyketide biosynthesis, unprecedented metal-catalysed Doebner-Knoevenagel condensations between Malonic Acid Half Thioesters (MAHTs) and various aldehydes have been achieved through the use of Yb(OTf)3 as catalyst, mimicking a five

An exceptionally mild catalytic thioester aldol reaction inspired by polyketide biosynthesis

This report details our discovery of a new catalytic ester aldol reaction using malonic acid half thioesters (MAHTs) that directly affords β-hydroxythioesters. The reaction is catalyzed by combination of a Cu(II) salt and an amine base, and it can be perf

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).

LITHIUM 1,8-DIAZABICYCLOUNDEC-7-EN-6-IDE AS NOVEL CARBON DIOXIDE CARRIER

Lithium 1,8-diazabicycloundec-7-en-6-ide (1) has underwent the insertion of carbon dioxide and the resulting lithium 6-carboxylato complex (2) transferred the carboxylato moiety to active methylene compounds (3) such as p-nitroacetophenone, acetophenone, p-methoxyacetophenone, and S-benzylthioacetate under mild conditions.

A Convenient Method for the Preparation of S-Esters of Thio Analogs of Malonic Acid

2-Carboxyethanethioic S-esters (RSCOCH2COOH) and propanebis(thioic) S,S'-diesters (RSCOCH2COSR) were easily prepared in high yields by the direct condensation of malonic acid with thiols in the presence of ethyl polyphosphate (PPE).

2-Morpholinoimidazolinomagnesium(II) Complex as a Novel Carbon Dioxide Carrier

The magnesium complex (1) has been found to undergo fixation of carbon dioxide and the resulting 1-carboxylato-complex (2) transfers the carboxylato group to active methylene compounds (3) including acetophenone, benzylideneacetone, β-ionone, and S-benzyl thioacetate, under mild conditions.