Simple synthesis of sakuranetin and selinone via a common intermediate, utilizing complementary regioselectivity in the deacetylation of naringenin triacetate

Yasunobu Yamashita, Kengo Hanaya, Mitsuru Shoji, Takeshi Sugai

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

Sakuranetin and selinone were successfully synthesized utilizing the regioselective deacetylation of naringenin triacetate. Deacetylation of the latter at C-7 with imidazole in 1,4-dioxane at 40°C furnished the corresponding diacetate in 80% yield. Methylation of the obtained free hydroxy group and subsequent removal of the remaining two acetyl groups gave sakuranetin, which was previously isolated as a phytoalexin against rice blast disease fungus, Pyricularia oryzae, in 71% overall yield. The same intermediate, naringenin triacetate, was subjected to transesterification with 2-propanol in tetrahydrofuran, catalyzed by Candida antarctica lipase B. A contrasting regioselective preference for C-4′ deacetylation was observed, giving an isomeric diacetate in 82% yield. Prenylation of the free hydroxy group under Mitsunobu conditions and subsequent deprotection furnished selinone, which was previously isolated from Monotes engleri and exhibits antifungal activity against Candida albicans, in 55% overall yield.

Original languageEnglish
Pages (from-to)961-965
Number of pages5
JournalChemical and Pharmaceutical Bulletin
Volume64
Issue number7
DOIs
Publication statusPublished - 2016

Fingerprint

Regioselectivity
Dipterocarpaceae
Prenylation
Methylation
2-Propanol
Mycoses
Candida
Transesterification
Fungi
Candida albicans
naringenin
sakuranetin
Oryza
imidazole
phytoalexins
tetrahydrofuran
1,4-dioxane
Candida antarctica lipase B

Keywords

  • Flavanone
  • Lipase-catalyzed transesterification
  • Regioselective deprotection

ASJC Scopus subject areas

  • Drug Discovery
  • Chemistry(all)

Cite this

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title = "Simple synthesis of sakuranetin and selinone via a common intermediate, utilizing complementary regioselectivity in the deacetylation of naringenin triacetate",
abstract = "Sakuranetin and selinone were successfully synthesized utilizing the regioselective deacetylation of naringenin triacetate. Deacetylation of the latter at C-7 with imidazole in 1,4-dioxane at 40°C furnished the corresponding diacetate in 80{\%} yield. Methylation of the obtained free hydroxy group and subsequent removal of the remaining two acetyl groups gave sakuranetin, which was previously isolated as a phytoalexin against rice blast disease fungus, Pyricularia oryzae, in 71{\%} overall yield. The same intermediate, naringenin triacetate, was subjected to transesterification with 2-propanol in tetrahydrofuran, catalyzed by Candida antarctica lipase B. A contrasting regioselective preference for C-4′ deacetylation was observed, giving an isomeric diacetate in 82{\%} yield. Prenylation of the free hydroxy group under Mitsunobu conditions and subsequent deprotection furnished selinone, which was previously isolated from Monotes engleri and exhibits antifungal activity against Candida albicans, in 55{\%} overall yield.",
keywords = "Flavanone, Lipase-catalyzed transesterification, Regioselective deprotection",
author = "Yasunobu Yamashita and Kengo Hanaya and Mitsuru Shoji and Takeshi Sugai",
year = "2016",
doi = "10.1248/cpb.c16-00190",
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journal = "Chemical and Pharmaceutical Bulletin",
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TY - JOUR

T1 - Simple synthesis of sakuranetin and selinone via a common intermediate, utilizing complementary regioselectivity in the deacetylation of naringenin triacetate

AU - Yamashita, Yasunobu

AU - Hanaya, Kengo

AU - Shoji, Mitsuru

AU - Sugai, Takeshi

PY - 2016

Y1 - 2016

N2 - Sakuranetin and selinone were successfully synthesized utilizing the regioselective deacetylation of naringenin triacetate. Deacetylation of the latter at C-7 with imidazole in 1,4-dioxane at 40°C furnished the corresponding diacetate in 80% yield. Methylation of the obtained free hydroxy group and subsequent removal of the remaining two acetyl groups gave sakuranetin, which was previously isolated as a phytoalexin against rice blast disease fungus, Pyricularia oryzae, in 71% overall yield. The same intermediate, naringenin triacetate, was subjected to transesterification with 2-propanol in tetrahydrofuran, catalyzed by Candida antarctica lipase B. A contrasting regioselective preference for C-4′ deacetylation was observed, giving an isomeric diacetate in 82% yield. Prenylation of the free hydroxy group under Mitsunobu conditions and subsequent deprotection furnished selinone, which was previously isolated from Monotes engleri and exhibits antifungal activity against Candida albicans, in 55% overall yield.

AB - Sakuranetin and selinone were successfully synthesized utilizing the regioselective deacetylation of naringenin triacetate. Deacetylation of the latter at C-7 with imidazole in 1,4-dioxane at 40°C furnished the corresponding diacetate in 80% yield. Methylation of the obtained free hydroxy group and subsequent removal of the remaining two acetyl groups gave sakuranetin, which was previously isolated as a phytoalexin against rice blast disease fungus, Pyricularia oryzae, in 71% overall yield. The same intermediate, naringenin triacetate, was subjected to transesterification with 2-propanol in tetrahydrofuran, catalyzed by Candida antarctica lipase B. A contrasting regioselective preference for C-4′ deacetylation was observed, giving an isomeric diacetate in 82% yield. Prenylation of the free hydroxy group under Mitsunobu conditions and subsequent deprotection furnished selinone, which was previously isolated from Monotes engleri and exhibits antifungal activity against Candida albicans, in 55% overall yield.

KW - Flavanone

KW - Lipase-catalyzed transesterification

KW - Regioselective deprotection

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