Stereoselective amination of 4-penten-1,2,3-triols; its synthetic application to (-)-anisomycin and (+)-polyoxamic acid = 4-펜텐-1,2,3-트리올의 입체선택적인 아민화 반응과 이를 이용한 (-)-아니 소마이신과 (+)-폴리옥사믹산의 합성

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The double bond of (2S, 3S)-4-penten-1,2,3-triol 28, which was readily prepared from dimethyl L-tartrate in 67% overall yield, was iodoaminated stereoselectively by treating its tris(trichloroacetimidate) with iodine monobromide. Also that of (2R, 3S)-4-penten-1,2,3-triol 84, which was produced from lactone 87 in 68% overall yield, was functionalized into amino iodide stereoselectively by cyclizing its tris(trichloroacetimidate) with iodine. After acidic hydrolysis of the cyclized products followed by protection as t-butyl carbamate, the former and the latter stereoselectivity were determined to be 37: 1 and 38: 1 in favor of (2S, 3S, 4S)- and (2R, 3S, 4S)-4-amino-5-iodo-1,2,3-triol, respectively. Since (-)-anisomycin 30 and (+)-polyoxamic acid 31 contain the fucntional groups of carbamate 29, their syntheses were accomplished efficiently from 29. Carbamate 29 was converted into triol 112 via its protection as acetonide, aziridine formation and cuprate reaction. Cyclization of 112 into pyrrolidine 104 proceeded smoothly under Mitsunobu conditions in the presence of PPTS. The adjustment of its functional groups established the synthesis of (-)-anisomycin 30. Monosilylation followed by acetonide formation gave iodide 116. Treatment of 116 with acetate generated oxazolidinone, of which protection and hydrolysis provided alcohol 119. The synthesis of (+)-polyoxamic acid 31 was completed by oxidation of 119 followed by acidic hydrolysis.
Advisors
Kang, Sung-Horesearcher강성호researcher
Description
한국과학기술원 : 화학과,
Publisher
한국과학기술원
Issue Date
1996
Identifier
105603/325007 / 000943560
Language
eng
Description

학위논문(석사) - 한국과학기술원 : 화학과, 1996.2, [ iii, 53 p. ]

Keywords

(-)-Anisomycin; 4-Penten-1,2,3-triol; Iodoamination; (+)-Polyoxamic acid; (+)-폴리옥사믹산; (-)-아니소마이신; 4-펜텐-1,2,3-트리올; 요드아민화반응

URI
http://hdl.handle.net/10203/32745
Link
http://library.kaist.ac.kr/search/detail/view.do?bibCtrlNo=105603&flag=dissertation
Appears in Collection
CH-Theses_Master(석사논문)
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