Accessing erythronolide structure space: new reactions and applications

An integrated routing strategy approach towards the synthesis of novel erythronolides is discussed in this dissertation. A macrocyclic bis[allene] compound was made as a synthetic scaffold. To date, more than 30 erythronolide derivatives have been made from this intermediate within 3 steps or less. This approach represents by far the most efficient and economic route for the access of erythronolide structure space. Many reactions were utilized in the modification of these 14-membered macrolides, including bromination, chelation and non-chelation controlled reductions and benzylic migration, elimination, etc. More importantly, novel allene oxidation conditions such as allene epoxidation, spirodiepoxidation, and osmylation, transformations developed by our group, were applied in the synthesis of diverse erythronolides and were central to our strategy. New reactions, including new procedures of allene dihydroxylation and allene osmylation-electrophile addition, are also discussed.Ph. D.Includes bibliographical referencesIncludes vitaby Kai Li