92595-26-1

Upstream product

• 54214-57-2 Ethyl α-(chloromethylthio)-acetate 
• 108-88-3 toluene 
• 104-81-4 4-Methylbenzyl bromide 
• 623-51-8 ethyl 2-sulfanylacetate 
• 623-73-4 diazoacetic acid ethyl ester 
• 4498-99-1 4-methylbenzylthiol 
• 141-97-9 ethyl acetoacetate 

Relevant academic research and scientific papers

Selective synthesis of α-organylthio esters and α-organylthio ketones from β-keto esters and sodium S-organyl sulfurothioates under basic conditions

We described herein a selective method to prepare α-organylthio esters and α-organylthio ketones by the reaction of β-keto esters with sodium S-benzyl sulfurothioate or sodium S-alkyl sulfurothioate (Bunte salts) under basic conditions in toluene as the solvent at 100 °C. When 4 equivalents of a base were used, a series of differently substituted α-thio esters were obtained with up to 90% yield. On the other hand, employing 2 equivalents of a base, α-thio ketones were achieved after 18 h under air. Furthermore, after a shorter reaction time, the isolation of keto-enol tautomers was possible, revealing them as significant intermediates for the mechanism elucidation.

MYOGLOBIN-BASED CATALYSTS FOR CARBENE TRANSFER REACTIONS

Methods are provided for carrying out carbene transfer transformations such as olefin cyclopropanation reactions, carbene heteroatom-H insertion reactions (heteroatom = N, S, Si), sigmatropic rearrangement reactions, and aldehyde olefination reactions with high efficiency and selectivity by using a novel class of myoglobin-based biocatalysts. These methods are useful for the synthesis of a variety of organic compounds which contain one or more new carbon-carbon or carbon-heteroatom (N, S, or Si) bond. The methods can be applied for conducting these transformations in vitro (i.e., using the biocatalyst in isolated form) and in vivo (i.e., using the biocatalyst in a whole cell system).

Intermolecular carbene S-H insertion catalysed by engineered myoglobin-based catalysts

The first example of a biocatalytic strategy for the synthesis of thioethers via an intermolecular carbene S-H insertion reaction is reported. Engineered variants of sperm whale myoglobin were found to efficiently catalyze this C-S bond forming transformation across a diverse set of aryl and alkyl mercaptan substrates and α-diazoester carbene donors, providing high conversions (60-99%) and high numbers of catalytic turnovers (1100-5400). Furthermore, the enantioselectivity of these biocatalysts could be tuned through mutation of amino acid residues within the distal pocket of the hemoprotein, leading to myoglobin variants capable of supporting asymmetric S-H insertions with up to 49% ee. Rearrangement experiments support a mechanism involving the formation of a sulfonium ylide generated upon attack of the thiol substrate to a heme-bound carbene intermediate. This journal is

Alkadiene derivatives, their preparation, and pharmaceutical compositions containing them

Substituted alkadienes of the formula: STR1 in which R1 is hydroxy or acetoxy, R2 is hydrogen, carboxy, alkoxycarbonyl, phenyl or benzoyl, and R3 is alkylthio or alkoxy and R4 is naphthoyl or optionally substituted benzoyl, or R3 is alkoxycarbonyl, cycloalkyloxycarbonyl or cyano and R4 is alkyl, naphthyl, optionally substituted phenyl, alkylthio, naphthylmethanethio, optionally substituted benzylthio, optionally substituted phenylthio, naphthylthio, phenethylthio or allylthio, or R3 and R4 form, with the carbon atom to which they are attached, a ring-system of formula: STR2 in which R5 is hydrogen or alkoxy and X is methylene or S inhibit 5-lipoxygenase and are useful, for example, as anti-inflammatories.

Monomethylation of Aromatic Rings by Friedel-Crafts Reaction with Chloromethyl Sulfide

A novel method for the introduction of a methyl group into aromatic rings is described.Friedel-Crafts reactions of ethyl α-(chloromethylthio)acetate (3k) and α-chloromethylthio-γ-butyrolactone (3m) with an arene in the presence of stannic chloride gave ethyl α-(arylmethylthio)acetate (6) and α-arylmethylthio-γ-butyrolactone (7), respectively, which were easily converted to the corresponding methylated arene (8) by reductive desulfurization with Raney nickel or zinc dust-acetic acid.Keywords - monomethylation; ethyl α-(chloromethylthio)acetate Friedel-Crafts reaction; α-chloromethylthio-γ-butyrolactone Friedel-Crafts reaction; ethyl α-(arylmethylthio)acetate; α-arylmethylthio-γ-butyrolactone; methylated arene; reductive desulfurization; Raney nickel; zinc dust-acetic acid