Of -acetomycin

Baeyer-Villiger oxidation has been used to selectively oxidize one of two methyl ketones (to esters) in the final step of a stereoselective synthesis of (—)-acetomycin, an antibiotic with potential anti-leukemia activity (equation 25)135. This reaction was accomplished using MCPBA as oxidant, with an excess of sodium bicarbonate and 5-/er/-bulyl-4-hydroxy-2-melhyl phenyl sulfide as a radical inhibitor. 

Ozonolysis also plays a key role in the stereoselective synthesis of acetomycin antibiotics. The densely functionalized acetomycin 75 has other stereochemical arrangements 76-78 of interest.72... 

Tadano, K, Ishihara, J, Ogawa, S, Total synthesis of (—)-acetomycin. Tetrahedron Lett., 31, 2609-2612, 1990. 

Additions of methyl 2-iodoalkanoates such as [5d] to vinyl acetate [22] afforded cyclic acylals such as [23] (Scheme 10). A large variety of acylals can be synthesized these may be of interest as analogs of acetomycin, a natural compound with antibiotic and antitumor activity (10). 

Sprules, T.J., and J.-F. Lavallee, Unexpected Contrasteric Alkylation Leading to a Model for Five-Membered Ring Enolate Alkylation Short Stereoselective Synthesis of ( )-Acetomycin, y. Org. Chem. 60 5041-5047 (1995). 

Along with the total synthesis of (—)-acetomycin, a highly functionalized y-lactone with antitumor activity, Kinderman and Feringa (98TA1215) described the stereoselective hydrogenation of the enantiomerically pure (-h)-(S)-5-acetoxy-2(5// )-furanone 123 in methanol at and in the presence of palladium on carbon ... 

A synthesis of acetomycin 35, together with three stereoisomers, has been achieved using the D-glucose-based precursor 34.22 yhe known branched glycoside 36 has been used in the synthesis of lactone 37 which has then been used, via a Pictet-Spengler cyclocondensation with trytamine, in a new approach to the corynantheine and heteroyohimbine classes of indole... 

In a multistep synthesis of (-)-acetomycin (31), which served to confirm its absolute configuration, the doubly-branched furanose (32) (Scheme 5), produced from D-glucose by a stereoselective Claisen rearrangement (Vol. 23, p. 150), was degraded to the intermediate (33), which was subsequently elaborated to the target (glucose carbons indicated). 5... 

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