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Method of synthesis of ciguatoxin ctx1b and compounds useful for the synthesis of ciguatoxin ctx1b

外国特許コード F110003706
整理番号 B32-01WO
掲載日 2011年7月4日
出願国 欧州特許庁(EPO)
出願番号 07706872
公報番号 1982988
公報番号 1982988
出願日 平成19年1月10日(2007.1.10)
公報発行日 平成20年10月22日(2008.10.22)
公報発行日 平成26年6月4日(2014.6.4)
国際出願番号 JP2007050545
国際公開番号 WO2007083638
国際出願日 平成19年1月10日(2007.1.10)
国際公開日 平成19年7月26日(2007.7.26)
優先権データ
  • 2007JP050545 (2007.1.10) WO
  • 特願2006-011297 (2006.1.19) JP
発明の名称 (英語) Method of synthesis of ciguatoxin ctx1b and compounds useful for the synthesis of ciguatoxin ctx1b
発明の概要(英語) Disclosed is a method for total synthesis of CTX1B, which is developed for the synthesis of a ciguatoxin analogue such as CTX3C and enables the more efficient application of an established reaction to the total synthesis of CTC1B.
More specifically, disclosed is a method for total synthesis of CTX1B comprising; an O.S-acetal formation for synthesizing a novel compound (3); a radical cyclization reaction for constructing a 9-membered ring formation reaction including a novel compound (6) through a novel compound (8) and yielding a compound (D); and a deprotection for yielding CTX1B.
Also disclosed are novel compounds (1) to (8) which are particularly useful for synthesis of CTX1B and can be used for the synthesis of a ciguatoxin analogue.
特許請求の範囲(英語) [claim1]
1. A method for preparation of CTX1B including following 10 processes, (see diagramm) a double bond of compound A (see diagramm) is oxidized by osmium tetra oxide and changed to diol derivative of compound A, transformed the diol to aldehyde by oxidation -cleavage by sodium periodate, then reduced the aldehyde to alcohol using sodium borohydride and obtain compound 1 (process 1), (see diagramm) alcohol of compound 1 is transformed to compound 2 using diphenyldisulfide . tributylphosphine (process 2), (see diagramm) said compound 2 is transformed to alpha chlorosulphide using N-chlorosuccinimide and synthesize compound B, (see diagramm) under the presence of DTBMP said compound B is joined to the ABCDE ring segments compound C as O,S-acetal using silver triflate and compound 3 is formed (process 3), (see diagramm) TIPS group of said compound 3 is removed using TBAF and form compound 4 (process 4), (see diagramm) pentafluorophenylpropiolate is joined to alcohol of said compound 4 using trimethylphosphine and compound 5 is formed (process 5), (see diagramm) carry out radical cyclizing reaction on said compound 5 by treating with AIBN and tintributyl hydride and form G ring part, so that compound 5 transforms to carboxylic acid compound D, then (see diagramm) transforms to methyl ester by acting trimethylsilyldiazomethane and forms compound 6 (process 6), (see diagramm) forms compound 7 (process 7) by reducing methyl ester of said compound 6 by diisobutylaluminum hydrate under lower temperature condition, then transforms to olefin by Wittig reaction, (see diagramm) forms compound 8 (process 8) by forming F ring part by carrying out ring closure methathesis reaction acting Grubbs catalyst to said compound 7, (see diagramm) synthesizes compound E, 1,2-diol of A ring side chain of which is protected by naphthylacetal, by oxidizing 6 NAP groups using DDQ and removing 5 NAP groups (process 9), then (see diagramm) carries out acid treatment on said compound E (process 10), wherein, in compounds A, B, D, E, CTX1B and compounds 1-8, NAP is 2-naphthylmethyl group, Me is methyl group, TIPS is triisopropylsilyl group, Ph is phenyl group, further, shortened mark DTBMP is 2,6-di-butyl-4-methylpyridine, TBAF is tetrabutylammonium fluoride, AIBN is alpha , alpha '-azobis(isobutyronitrile), DDQ is 2,3-dichloro-5,6-dicyano -1,4-benzoquinone.
  • 出願人(英語)
  • JAPAN SCIENCE AND TECHNOLOGY AGENCY
  • 発明者(英語)
  • HIRAMA MASAHIRO
  • INOUE MASAYUKI
国際特許分類(IPC)
欧州特許分類/主・副
  • C07D493/22
  • C07D519/00
  • C07F007/18C4D4D
指定国 Contracting States: ES FR
参考情報 (研究プロジェクト等) SORST Selected in Fiscal 2002
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