96096-72-9

Upstream product

• 56958-97-5 (2R,3S)-dimethyl oxirane-2,3-dicarboxylate 
• 75-91-2 tert.-butylhydroperoxide 
• 624-48-6 dimethyl cis-but-2-ene-1,4-dioate 
• 67-56-1 methanol 
• 16191-17-6 cis-2,3-epoxysuccinic anhydride 

Downstream Products

• 112545-72-9 (2S,3S)-3-((S)-Hydroxy-methoxycarbonyl-methyl)-1-(4-methoxy-phenyl)-4-oxo-azetidine-2-carboxylic acid 
• 112545-73-0 (S)-[(2R,3R)-2-Acetoxy-1-(4-methoxy-phenyl)-4-oxo-azetidin-3-yl]-hydroxy-acetic acid methyl ester 
• 112545-70-7 (2S,3S)-3-((S)-Hydroxy-methoxycarbonyl-methyl)-1-(4-methoxy-phenyl)-4-oxo-azetidine-2-carboxylic acid tert-butyl ester 
• 112545-74-1 (R)-[(2S,3S)-2-Acetoxy-1-(4-methoxy-phenyl)-4-oxo-azetidin-3-yl]-(tert-butyl-dimethyl-silanyloxy)-acetic acid methyl ester 
• 112545-78-5 (2R,5R,6S)-6-((S)-Hydroxy-methoxycarbonyl-methyl)-3,7-dioxo-1-aza-bicyclo[3.2.0]heptane-2-carboxylic acid 4-nitro-benzyl ester 
• 112545-79-6 (5R,6S)-6-((S)-Hydroxy-methoxycarbonyl-methyl)-7-oxo-3-(pyridin-4-ylsulfanyl)-1-aza-bicyclo[3.2.0]hept-2-ene-2-carboxylic acid 4-nitro-benzyl ester 
• 112545-69-4 (2RS,3SR)-N-(t-butoxycarbonylmethyl)-N-(4-methoxyphenyl)-3-methoxycarbonyl-2,3-epoxypropionate 
• 112545-69-4 (2R,3S)-3-[tert-Butoxycarbonylmethyl-(4-methoxy-phenyl)-carbamoyl]-oxirane-2-carboxylic acid methyl ester 

Relevant academic research and scientific papers

Preparation of dicarboxylate analogues of Cerulenin

We have proposed and synthesized several new structural classes of Cerulenin analogues, which have potential as inhibitors of both fatty acid and polyketide synthase multi-enzyme complexes. These analogues contain cis epoxides bearing flanking carboxylate groups. Our syntheses have been designed to allow access to a wide range of fatty acid and polyketide-like side chains from readily available starting materials in convergent fashion in just four to five steps. In total, ～40 potential analogues have been prepared and characterized, covering all the structural sub-classes proposed, the majority of which constitute novel functional groupings.

Synthesis of an optically active 4-acetoxyazetidinone intermediate for penems and carbapenems

The synthesis of the novel (3R,4R)-4-acetoxy-3[(1S)-1-t-butyldimethylsilyloxymethyl-1-((1S)-1-ph nylethylaminocarbonyl)]azetidin-2-one, a valuable key intermediate for penems and carbapenems bearing a 6-hydroxyacetamide side chain, and its diastereomer 1b

A stereocontrolled approach to electrophilic epoxides

Lithium t-butyl hydroperoxide (easily generated by addition of an alkyl-lithium to anhydrous t-butyl hydroperoxide in THF solution) is a powerful reagent for the epoxidation of electrophilic alkenes at -20 to 0 °C under full stereocontrol. Thus αβ-unsaturated esters, sulphones, sulphoximines, and amides are readily epoxidised with complete regio- and stereo-specificity and with considerable chiroselectivity (20-100%) when appropriate chiral auxiliaries such as menthyl, 8-phenylmenthyl, or a camphor-sulphonamide derivative are used. Asymmetric αβ-unsaturated sulphoximines undergo epoxidation with 100% diastereoselectivity. The only exceptions to stereocontrol noted are heavily substituted maleate esters such as di-t-butyl maleate. The αβ-epoxy amides are shown to be valuable sources of the corresponding epoxy ketones by treatment with an organolithium, allowing a stereo- and chemoselective entry in high yield to these useful intermediates.

SYNTHESIS OF A NEW CARBAPENEM WITH A 6-METHYL HYDROXYACETATE SIDE CHAIN

The synthesis of the 2-(4-pyridinylthio)-carbapen-2-em-3-carboxylic acid 1b, bearing a 6-methyl hydroxyacetate side chain, is decribed.