205584-89-0

Upstream product

• 541-47-9 3-Methylbutenoic acid 
• 100-39-0 benzyl bromide 
• 184528-76-5 (R)-benzyl 2,3-dihydroxy-3-methylbutanoate 
• 37526-89-9 benzyl 3-methylbut-2-enoate 
• 184528-78-7 (R)-1-((benzyloxy)carbonyl)-2-hydroxy-2-methylpropyl methanesulfonate 

Downstream Products

• 184758-45-0 (S)-Hydroxy-((R)-2-methyl-oxiranyl)-acetic acid benzyl ester 
• 127661-26-1 benzyl (2S,3S)-3,4-epoxy-2-(3-methoxy-5-methyl-1-naphthoyloxy)-3-methylbutanoate 
• 205584-90-3 Naphthalene-1-carboxylic acid (S)-benzyloxycarbonyl-((S)-2-methyl-oxiranyl)-methyl ester 
• 127661-25-0 (S)-benzyl 2-hydroxy-2-((S)-2-methyloxiran-2-yl)acetate 
• 157087-28-0 (S)-benzyl 2-hydroxy-3-methylbut-3-enoate 

Relevant academic research and scientific papers

Exploration of the molecular origin of the azinomycin epoxide: Timing of the biosynthesis revealed

(Equation Presented) Streptomyces sahachiroi whole cell feeding experiments, utilizing putative precursors labeled with stable isotopes, established that the epoxide unit of the DNA cross-linked agents, azinomycin A and B, proceeds via a valine-dependent pathway and that hydroxylation and dehydration precedes formation of the terminal epoxide. Sodium 3-methyl-2-oxobutenoate, formed through a transimination reaction, was shown to be the penultimate precursor incorporated into the azinomycin epoxide.

Asymmetric synthesis of the left hand portion of the azinomycins

A nine step synthesis of the left hand portion of the azinomycins is described starting from 3,3-dimethyl-acrylic acid. The approach relies on a Sharpless asymmetric dihydroxylation (AD) reaction to install the requisite (2S,3S)-stereochemistry of epoxy alcohol 4. This epoxide is converted to crystalline amide derivative 12 whose structure and absolute stereochemistry have been unambiguously established using X-ray crystallography. Coupling of epoxy alcohol (2S,3S)-4 with naphthoyl chloride 16 and subsequent manipulations furnish epoxy amide (2S,3S)-1 identical in all respects with the natural material.