The Catalytic Alkylative Desymmetrization of Anhydrides in a Formal Synthesis of Ionomycin

The catalytic desymmetrization of anhydrides with zinc reagents provides access to deoxypolypropionate and polypropionate synthons. A synthesis of ionomycin was pursued in which three of the four fragments were assembled using this methodology. Two of the strategies (enol silane/oxocarbenium couplin...

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Bibliographic Details
Published inSynthesis (Stuttgart) Vol. 50; no. 22; pp. 4343 - 4350
Main Authors Oberg, Kevin M., Cochran, Brian M., Cook, Matthew J., Rovis, Tomislav
Format Journal Article
LanguageEnglish
Published STUTTGART Thieme Medical Publishers 01.11.2018
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
enantioselective synthesis
anhydride desymmetrization
POLYETHER ANTIBIOTIC IONOMYCIN
4 STEREOCENTERS
ASYMMETRIC-SYNTHESIS
diastereoselectivity
ENANTIOSELECTIVE DESYMMETRIZATION
GENERAL STRATEGY
HEPTANE BUILDING-BLOCKS
SINGLE CHIRAL PROGENITOR
FRAGMENT
total synthesis
STEREOSELECTIVE-SYNTHESIS
rhodium
SUBUNIT
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Summary:The catalytic desymmetrization of anhydrides with zinc reagents provides access to deoxypolypropionate and polypropionate synthons. A synthesis of ionomycin was pursued in which three of the four fragments were assembled using this methodology. Two of the strategies (enol silane/oxocarbenium coupling and reductive cyclization) were not successful at installing the C23 stereocenter, but this stereochemical issue was overcome through a reduction/SN2 approach. In addition to the synthesis of a protected diastereomer of ionomycin, the synthesis of a C17-C32 fragment constitutes a formal total synthesis.
ISSN:0039-7881
1437-210X
DOI:10.1055/s-0037-1610108