Total synthesis of (+)-asteltoxin.
A convergent synthesis of (+)-asteltoxin (1) has been achieved by the Horner-Emmons olefination of bis(tetrahydrofuran) aldehyde 53 and alpha-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.
Eom
Khee Dong
KD
Department of Chemistry, University of Alabama, Tuscaloosa, Alabama 35487, USA.
Raman
J Venkat
JV
Kim
Heejin
H
Cha
Jin Kun
JK
D001230:Aspergillus / Q000737:chemistry; D009183:Mycotoxins / Q000138:chemical synthesis*; D011753:Pyrones / Q000138:chemical synthesis*; D013237:Stereoisomerism
D009183:Mycotoxins; D011753:Pyrones; C030923:asteltoxin