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Article Abstract
For the first time, we describe the stereocontrolled total syntheses of olivil, cephafortin A, 4-des--methyl-4--rhamnosyl cephafortin A, and alashinol F from a common precursor using a combination of chemoenzymatic and biomimetic methods for the systematic introduction of functional groups on three vicinal stereogenic carbon atoms. We revised the previously assigned stereochemistry of (+)-cephafortin A, which was reported as the enantiomer. Natural and unnatural congeners provide insights into the biogenetic interrelations of members of this family.
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