185515-96-2

Upstream product

• 72526-00-2 (-)-8-phenylmenthyl acrylate 
• 84312-20-9 (1R,3R,4S)-8-phenylmenthyl glyoxylate 
• 65253-04-5 (-)-8-phenylmenthol 
• 177285-57-3 1-(1,3-dioxolan-2-ylidene)-5-hexen-2-one 
• 185515-94-0 <1R-(1α,2β,5α)>-5-methyl-2-(1-methyl-1-phenylethyl)cyclohexyl 2-hydroxy-3-nitropropanoate 
• 185515-93-9 <1R-<1α(E),2β,5α>>-5-methyl-2-(1-methyl-1-phenylethyl)cyclohexyl 3-nitro-2-propenoate 
• 185515-92-8 ((Z)-1-[1,3]Dioxolan-2-ylidenemethyl-penta-1,4-dienyloxy)-trimethyl-silane 
• 185515-95-1 <6S-<6α,7β,(1S^*,2R^*,5S^*),8β>>-5-methyl-2-(1-methyl-1-phenylethyl)cyclohexyl 6-nitro-9-oxo-8-(2-propenyl)-1,4-dioxaspiro<4.5>decane-7-carboxylate 

Downstream Products

• 185515-97-3 <6S-<6α,7β,(1S^*,2R^*,5S^*),8β>>-5-methyl-2-(1-methyl-1-phenylethyl)cyclohexyl 9-<<(1,1-dimethylethyl)dimethylsilyl>oxy>-6-nitro-8-(2-propenyl)-1,4-dioxaspiro<4.5>decane-7-carboxylate 

Relevant academic research and scientific papers

Synthesis and X-ray crystal structure of (-)-calicheamicinone

Diels-Alder reaction between ketene acetal 3 and the β-nitroacrylate ester 12 of (-)-8-phenylmenthol gave optically pure ketone 17. This substance was modified in such a way as to remove the chiral auxiliary and afford the epimeric silyl ethers 20M and 20m. Following procedures worked out using racemic materials, both 20M and 20m were converted into optically pure (-)- calicheamicinone (1). This is a crystalline substance, and an X-ray structure determination was carried out.

Formal synthesis of (-)-calicheamicinone and of (+)-calicheamicinone

An asymmetric Diels-Alder reaction between ketene acetal 2 and the 3-nitropropenoate 10, derived from (-)-8-phenyl-menthol, affords the optically pure adduct 15, which can be converted into either enantiomer of calicheamicinone 1.