Reinvestigation of the Biomimetic Cyclization of 3,5-Diketo Esters: Application to the Total Synthesis of Cyercene A, an α-Methoxy-γ-Pyrone-Containing Polypropionate

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Abstract

The biomimetic cyclization of 3,5-diketo esters was reinvestigated for the synthesis of α-methoxy-γ-pyrones. 3,5-Diketo esters were selectively synthesized via the aldol reaction of commercially available methyl 2-methyl-3-oxopentanoate with an aldehyde followed by the oxidation with AZADOL® and PhI(OAc)2. The DBU-promoted intramolecular transesterification of 3,5-diketo esters showed excellent reactivity in MeOH, to give the corresponding γ-hydroxy-α-pyrones in high yields under mild reaction conditions. Based on the present cyclization scheme, the total synthesis of cyercene A was achieved.

Original languageEnglish
JournalSynlett
DOIs
Publication statusAccepted/In press - Mar 26 2017

Fingerprint

Pyrones
Cyclization
Biomimetics
Esters
Transesterification
Aldehydes
Oxidation
cyercene A

Keywords

  • 3,5-diketo esters
  • cyercene A
  • intramolecular transesterification
  • polyketide
  • γ-pyrone

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

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title = "Reinvestigation of the Biomimetic Cyclization of 3,5-Diketo Esters: Application to the Total Synthesis of Cyercene A, an α-Methoxy-γ-Pyrone-Containing Polypropionate",
abstract = "The biomimetic cyclization of 3,5-diketo esters was reinvestigated for the synthesis of α-methoxy-γ-pyrones. 3,5-Diketo esters were selectively synthesized via the aldol reaction of commercially available methyl 2-methyl-3-oxopentanoate with an aldehyde followed by the oxidation with AZADOL{\circledR} and PhI(OAc)2. The DBU-promoted intramolecular transesterification of 3,5-diketo esters showed excellent reactivity in MeOH, to give the corresponding γ-hydroxy-α-pyrones in high yields under mild reaction conditions. Based on the present cyclization scheme, the total synthesis of cyercene A was achieved.",
keywords = "3,5-diketo esters, cyercene A, intramolecular transesterification, polyketide, γ-pyrone",
author = "Kai Onda and Ichiro Hayakawa and Akira Sakakura",
year = "2017",
month = "3",
day = "26",
doi = "10.1055/s-0036-1588795",
language = "English",
journal = "Synlett",
issn = "0936-5214",
publisher = "Georg Thieme Verlag",

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T1 - Reinvestigation of the Biomimetic Cyclization of 3,5-Diketo Esters

T2 - Application to the Total Synthesis of Cyercene A, an α-Methoxy-γ-Pyrone-Containing Polypropionate

AU - Onda, Kai

AU - Hayakawa, Ichiro

AU - Sakakura, Akira

PY - 2017/3/26

Y1 - 2017/3/26

N2 - The biomimetic cyclization of 3,5-diketo esters was reinvestigated for the synthesis of α-methoxy-γ-pyrones. 3,5-Diketo esters were selectively synthesized via the aldol reaction of commercially available methyl 2-methyl-3-oxopentanoate with an aldehyde followed by the oxidation with AZADOL® and PhI(OAc)2. The DBU-promoted intramolecular transesterification of 3,5-diketo esters showed excellent reactivity in MeOH, to give the corresponding γ-hydroxy-α-pyrones in high yields under mild reaction conditions. Based on the present cyclization scheme, the total synthesis of cyercene A was achieved.

AB - The biomimetic cyclization of 3,5-diketo esters was reinvestigated for the synthesis of α-methoxy-γ-pyrones. 3,5-Diketo esters were selectively synthesized via the aldol reaction of commercially available methyl 2-methyl-3-oxopentanoate with an aldehyde followed by the oxidation with AZADOL® and PhI(OAc)2. The DBU-promoted intramolecular transesterification of 3,5-diketo esters showed excellent reactivity in MeOH, to give the corresponding γ-hydroxy-α-pyrones in high yields under mild reaction conditions. Based on the present cyclization scheme, the total synthesis of cyercene A was achieved.

KW - 3,5-diketo esters

KW - cyercene A

KW - intramolecular transesterification

KW - polyketide

KW - γ-pyrone

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