P-56 アミノ糖系抗生物質の合成研究(ポスター発表の部)

• 楠本 善史

  高知大院理

• 奥村 健

  高知大院理

• 原 加那子

  高知大院理

• 市川 善康

  高知大院理

• 西山 泰平

  名大院生命農

• 磯部 稔

  名大院生命農

書誌事項

タイトル別名

• P-56 Synthetic Studies of Aminosugar Antibiotics

抄録

Glycocinnasperimicin D (1) was isolated from the fermentation broth of the producing strain (Nocardia) and its structure was elucidated by spectroscopic studies by Umezawa and his co-workers. Structurally, glycocinnasperimicin D contains two highly functionalized aminosugars, that is, the left portion is 2-ureido-pentose and the right part is 2-guanidino-4-ureido-6-deoxy-a-D-glucopyranose with p-cinnamoylspermidine aglycon. Moreover, these two unusual aminosugars are joined with unique glycosyl-urea linkage. Synthesis of the right portion of aminosugar A commenced with D-glucosamine hydrochloride (4). Lewis acid-catalyzed phenyl glycosidation provided a-phenyl glycoside 6. Tosylation and protection of C-3 hydroxy group gave 7, which was, subjected by displacement reaction with iodide anion and reductive hydrogenolysis to afford 6-deoxy pyranose 8. Further protective group manipulation gave rise to 13, which underwent the Heck reaction with acrylyl-di-tert-butoxycarbonyl spermidine 14 to give rise to the cinnamoyl galactoside 15. Deprotection of the Troc-carbamate in 15 followed by treatment of the resultant amine with N,N-di-(tert-butoxycarbony1)-S-methyl isothiourea and mercuric chloride afforded bis(Boc)-protected guanidine 16. Introduction of the amino group at C-4 was achieved by the S_N2 displacement reaction of the triflate with azide anion to furnish 17. Synthesis of the left portion of aminosugar B began with the stereoselective synthesis of allyl amine based on the protocol recently developed in our group to afford 27 (Scheme 4). Further manipulation of 27 furnished the isonitrile glycoside 31(Scheme 5). Oxidation of the isonitrile 31 generated the isocyanate 2, which was subsequently treated with aminosugar 3 to afford the desired coupling product 34. Introduction of urea moiety and global deprotection for the total synthesis of glycocinnasperimicin D is underway.

収録刊行物

• 天然有機化合物討論会講演要旨集

  天然有機化合物討論会講演要旨集 49 (0), 643-648, 2007

  天然有機化合物討論会実行委員会

詳細情報

• CRID: 1390282681056294016
• NII論文ID: 110006682839
• DOI: 10.24496/tennenyuki.49.0_643
• ISSN: 24331856
• 本文言語コード: ja
• データソース種別:
  • JaLC
  • CiNii Articles
• 抄録ライセンスフラグ: 使用不可