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

Kai Onda; Ichiro Hayakawa; Akira Sakakura

doi:10.1055/s-0036-1588795

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

Kai Onda, Ichiro Hayakawa, Akira Sakakura

School of Engineering

Research output: Contribution to journal › Article › peer-review

3 Citations (Scopus)

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 language	English
Pages (from-to)	1596-1600
Number of pages	5
Journal	Synlett
Volume	28
Issue number	13
DOIs	https://doi.org/10.1055/s-0036-1588795
Publication status	Published - Aug 14 2017

Keywords

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

ASJC Scopus subject areas

Organic Chemistry

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10.1055/s-0036-1588795

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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 {\textregistered} 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",

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doi = "10.1055/s-0036-1588795",

language = "English",

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AU - Onda, Kai

AU - Hayakawa, Ichiro

AU - Sakakura, Akira

N1 - Publisher Copyright: © Georg Thieme Verlag Stuttgart. New York.

PY - 2017/8/14

Y1 - 2017/8/14

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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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

Keywords

ASJC Scopus subject areas

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