Total Synthesis of Pentamycin by a Conformationally Biased Double Stille Ring Closure with a Trienyl-bis-stannane.
J Am Chem Soc
; 145(20): 10974-10979, 2023 May 24.
Article
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| MEDLINE
| ID: mdl-37162233
ABSTRACT
The total synthesis of the potent polyene macrolide antibiotic pentamycin was accomplished by an expedient strategy involving a highly stereoselective assembly of the polyol segment in combination with an adventurous double Stille cross-coupling with a trienyl-bis-stannane closing the macrolactone and installing the sensitive pentaene fragment. Presumably, this remarkable linchpin insertion is enhanced by the linear hydrogen bonding skeleton of the polyol substrate. Further key features include a tailored Rychnovsky alkylation of cyanohydrin acetonides and elaborate Krische couplings to set the characteristic hydroxyl and hydroxymethyl bearing centers with excellent selectivity and yield. The total synthesis unequivocally confirms the full relative and absolute stereochemistry of this polyketide, including a previously uncertain hydroxyl bearing center.
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MEDLINE
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En
Ano de publicação:
2023
Tipo de documento:
Article