Synthesis of Saxitoxin and Its Derivatives

Yuya Okuyama; Ryosuke Okamoto; Shori Mukai; Kyoko Kinoshita; Takaaki Sato; Noritaka Chida

doi:10.1021/acs.orglett.0c03281

Synthesis of Saxitoxin and Its Derivatives

Yuya Okuyama, Ryosuke Okamoto, Shori Mukai, Kyoko Kinoshita, Takaaki Sato, Noritaka Chida

Department of Applied Chemistry

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

1 Citation (Scopus)

Abstract

The chiral synthesis of (+)-saxitoxin and its derivatives is described. Two consecutive carbon-nitrogen bonds at C-5 and C-6 in saxitoxin were effectively installed by the sequential Overman rearrangement of an allylic vicinal diol derived from d-malic acid. The bicyclic guanidine unit was constructed by the intramolecular aminal formation of an acyclic bis-guanidine derivative possessing a ketone carbonyl at C-4. From the bicyclic aminal intermediate, (+)-saxitoxin, (+)-decarbamoyl-β-saxitoxinol [(+)-dc-β-saxitoxinol], and the unnatural skeletal isomer, (-)-iso-dc-saxitoxinol, were synthesized.

Original language	English
Journal	Organic Letters
DOIs	https://doi.org/10.1021/acs.orglett.0c03281
Publication status	Accepted/In press - 2020

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry

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title = "Synthesis of Saxitoxin and Its Derivatives",

abstract = "The chiral synthesis of (+)-saxitoxin and its derivatives is described. Two consecutive carbon-nitrogen bonds at C-5 and C-6 in saxitoxin were effectively installed by the sequential Overman rearrangement of an allylic vicinal diol derived from d-malic acid. The bicyclic guanidine unit was constructed by the intramolecular aminal formation of an acyclic bis-guanidine derivative possessing a ketone carbonyl at C-4. From the bicyclic aminal intermediate, (+)-saxitoxin, (+)-decarbamoyl-β-saxitoxinol [(+)-dc-β-saxitoxinol], and the unnatural skeletal isomer, (-)-iso-dc-saxitoxinol, were synthesized. ",

author = "Yuya Okuyama and Ryosuke Okamoto and Shori Mukai and Kyoko Kinoshita and Takaaki Sato and Noritaka Chida",

note = "Funding Information: This research was supported by a JSPS Research Fellowships for Young Scientists to Y.O. (19J12788).",

year = "2020",

doi = "10.1021/acs.orglett.0c03281",

language = "English",

journal = "Organic Letters",

issn = "1523-7060",

publisher = "American Chemical Society",

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T1 - Synthesis of Saxitoxin and Its Derivatives

AU - Okuyama, Yuya

AU - Okamoto, Ryosuke

AU - Mukai, Shori

AU - Kinoshita, Kyoko

AU - Sato, Takaaki

AU - Chida, Noritaka

N1 - Funding Information: This research was supported by a JSPS Research Fellowships for Young Scientists to Y.O. (19J12788).

PY - 2020

Y1 - 2020

N2 - The chiral synthesis of (+)-saxitoxin and its derivatives is described. Two consecutive carbon-nitrogen bonds at C-5 and C-6 in saxitoxin were effectively installed by the sequential Overman rearrangement of an allylic vicinal diol derived from d-malic acid. The bicyclic guanidine unit was constructed by the intramolecular aminal formation of an acyclic bis-guanidine derivative possessing a ketone carbonyl at C-4. From the bicyclic aminal intermediate, (+)-saxitoxin, (+)-decarbamoyl-β-saxitoxinol [(+)-dc-β-saxitoxinol], and the unnatural skeletal isomer, (-)-iso-dc-saxitoxinol, were synthesized.

AB - The chiral synthesis of (+)-saxitoxin and its derivatives is described. Two consecutive carbon-nitrogen bonds at C-5 and C-6 in saxitoxin were effectively installed by the sequential Overman rearrangement of an allylic vicinal diol derived from d-malic acid. The bicyclic guanidine unit was constructed by the intramolecular aminal formation of an acyclic bis-guanidine derivative possessing a ketone carbonyl at C-4. From the bicyclic aminal intermediate, (+)-saxitoxin, (+)-decarbamoyl-β-saxitoxinol [(+)-dc-β-saxitoxinol], and the unnatural skeletal isomer, (-)-iso-dc-saxitoxinol, were synthesized.

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