American Chemical Society
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Total Synthesis of (+)-Asteltoxin

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journal contribution
posted on 2003-04-09, 00:00 authored by Khee Dong Eom, J. Venkat Raman, Heejin Kim, Jin Kun Cha
A convergent synthesis of (+)-asteltoxin (1) has been achieved by the Horner−Emmons olefination of bis(tetrahydrofuran) aldehyde 53 and α-pyrone phosphonate 5. A key step features the stereoselective construction of a sterically congested quaternary center embedded in the densely functionalized bis(tetrahydrofuran) subunit by a Lewis acid-catalyzed, pinacol-type rearrangement of an epoxy silyl ether. This pivotal rearrangement methodology parallels the proposed biosynthetic pathway of 1 and is ripe for applications to the stereocontrolled synthesis of structurally complex natural products.