Total Synthesis of 6-Deoxydihydrokalafungin, a Key Biosynthetic Precursor of Actinorhodin, and Its Epimer

In this article, we report the total synthesis of 6-deoxydihydrokalafungin (DDHK), a key biosynthetic intermediate of a dimeric benzoisochromanequinone antibiotic, actinorhodin (ACT), and its epimer, <i>epi</i>-DDHK. Tricyclic hemiacetal with 3-siloxyethyl group was subjected to Et<su...

Descripción completa

Guardado en:

Detalles Bibliográficos
Autores principales:	Takuya Kumamoto, Mika Kainuma, Azusa Takahashi, Yoshika Matsuo, Kazuaki Katakawa, Takaaki Taguchi, Koji Ichinose
Formato:	article
Lenguaje:	EN
Publicado:	MDPI AG 2021
Materias:	benzoisochromane diastereoselective reduction annulation deoxydihydrokalafungin actinorhodin Organic chemistry QD241-441
Acceso en línea:	https://doaj.org/article/95b1e4ae72584a8a99ccff564079d48e
Etiquetas:	Agregar Etiqueta Sin Etiquetas, Sea el primero en etiquetar este registro!

id	oai:doaj.org-article:95b1e4ae72584a8a99ccff564079d48e
record_format	dspace
spelling	oai:doaj.org-article:95b1e4ae72584a8a99ccff564079d48e2021-11-11T18:25:14ZTotal Synthesis of 6-Deoxydihydrokalafungin, a Key Biosynthetic Precursor of Actinorhodin, and Its Epimer10.3390/molecules262163971420-3049https://doaj.org/article/95b1e4ae72584a8a99ccff564079d48e2021-10-01T00:00:00Zhttps://www.mdpi.com/1420-3049/26/21/6397https://doaj.org/toc/1420-3049In this article, we report the total synthesis of 6-deoxydihydrokalafungin (DDHK), a key biosynthetic intermediate of a dimeric benzoisochromanequinone antibiotic, actinorhodin (ACT), and its epimer, <i>epi</i>-DDHK. Tricyclic hemiacetal with 3-siloxyethyl group was subjected to Et<sub>3</sub>SiH reduction to establish the 1,3-<i>cis</i> stereochemistry in the benzoisochromane, and a subsequent oxidation/deprotection sequence then afforded <i>epi</i>-DDHK. A bicyclic acetal was subjected to AlH<sub>3</sub> reduction to deliver the desired 1,3-<i>trans</i> isomer in an approximately 3:1 ratio, which was subjected to a similar sequence to that used for the 1,3-<i>cis</i> isomer that successfully afforded DDHK. A semisynthetic approach from (<i>S</i>)-DNPA, an isolable biosynthetic precursor of ACT, was also examined to afford DDHK and its epimer, which are identical to the synthetic products.Takuya KumamotoMika KainumaAzusa TakahashiYoshika MatsuoKazuaki KatakawaTakaaki TaguchiKoji IchinoseMDPI AGarticlebenzoisochromanediastereoselective reductionannulationdeoxydihydrokalafunginactinorhodinOrganic chemistryQD241-441ENMolecules, Vol 26, Iss 6397, p 6397 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	benzoisochromane diastereoselective reduction annulation deoxydihydrokalafungin actinorhodin Organic chemistry QD241-441
spellingShingle	benzoisochromane diastereoselective reduction annulation deoxydihydrokalafungin actinorhodin Organic chemistry QD241-441 Takuya Kumamoto Mika Kainuma Azusa Takahashi Yoshika Matsuo Kazuaki Katakawa Takaaki Taguchi Koji Ichinose Total Synthesis of 6-Deoxydihydrokalafungin, a Key Biosynthetic Precursor of Actinorhodin, and Its Epimer
description	In this article, we report the total synthesis of 6-deoxydihydrokalafungin (DDHK), a key biosynthetic intermediate of a dimeric benzoisochromanequinone antibiotic, actinorhodin (ACT), and its epimer, <i>epi</i>-DDHK. Tricyclic hemiacetal with 3-siloxyethyl group was subjected to Et<sub>3</sub>SiH reduction to establish the 1,3-<i>cis</i> stereochemistry in the benzoisochromane, and a subsequent oxidation/deprotection sequence then afforded <i>epi</i>-DDHK. A bicyclic acetal was subjected to AlH<sub>3</sub> reduction to deliver the desired 1,3-<i>trans</i> isomer in an approximately 3:1 ratio, which was subjected to a similar sequence to that used for the 1,3-<i>cis</i> isomer that successfully afforded DDHK. A semisynthetic approach from (<i>S</i>)-DNPA, an isolable biosynthetic precursor of ACT, was also examined to afford DDHK and its epimer, which are identical to the synthetic products.
format	article
author	Takuya Kumamoto Mika Kainuma Azusa Takahashi Yoshika Matsuo Kazuaki Katakawa Takaaki Taguchi Koji Ichinose
author_facet	Takuya Kumamoto Mika Kainuma Azusa Takahashi Yoshika Matsuo Kazuaki Katakawa Takaaki Taguchi Koji Ichinose
author_sort	Takuya Kumamoto
title	Total Synthesis of 6-Deoxydihydrokalafungin, a Key Biosynthetic Precursor of Actinorhodin, and Its Epimer
title_short	Total Synthesis of 6-Deoxydihydrokalafungin, a Key Biosynthetic Precursor of Actinorhodin, and Its Epimer
title_full	Total Synthesis of 6-Deoxydihydrokalafungin, a Key Biosynthetic Precursor of Actinorhodin, and Its Epimer
title_fullStr	Total Synthesis of 6-Deoxydihydrokalafungin, a Key Biosynthetic Precursor of Actinorhodin, and Its Epimer
title_full_unstemmed	Total Synthesis of 6-Deoxydihydrokalafungin, a Key Biosynthetic Precursor of Actinorhodin, and Its Epimer
title_sort	total synthesis of 6-deoxydihydrokalafungin, a key biosynthetic precursor of actinorhodin, and its epimer
publisher	MDPI AG
publishDate	2021
url	https://doaj.org/article/95b1e4ae72584a8a99ccff564079d48e
work_keys_str_mv	AT takuyakumamoto totalsynthesisof6deoxydihydrokalafunginakeybiosyntheticprecursorofactinorhodinanditsepimer AT mikakainuma totalsynthesisof6deoxydihydrokalafunginakeybiosyntheticprecursorofactinorhodinanditsepimer AT azusatakahashi totalsynthesisof6deoxydihydrokalafunginakeybiosyntheticprecursorofactinorhodinanditsepimer AT yoshikamatsuo totalsynthesisof6deoxydihydrokalafunginakeybiosyntheticprecursorofactinorhodinanditsepimer AT kazuakikatakawa totalsynthesisof6deoxydihydrokalafunginakeybiosyntheticprecursorofactinorhodinanditsepimer AT takaakitaguchi totalsynthesisof6deoxydihydrokalafunginakeybiosyntheticprecursorofactinorhodinanditsepimer AT kojiichinose totalsynthesisof6deoxydihydrokalafunginakeybiosyntheticprecursorofactinorhodinanditsepimer
_version_	1718431838411685888

Total Synthesis of 6-Deoxydihydrokalafungin, a Key Biosynthetic Precursor of Actinorhodin, and Its Epimer

Ejemplares similares