Synthetic studies on laidlomycin = 레이드로마이신의 합성에 관한 연구

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Highly enantioselective synthesis of the key intermediate 258 to laidlomycin 1 was established. 258 was disconnected to give the left segment containing of protected anti-, syn-1,3,5-triol and the right segment containing 3 oxacycles: successive cis-, trans-THF ring and 6-memebered cyclic ketal.The backbone of right segment (C11-26) was achieved by two B-alkyl Suzuki-Miyaura coupling reactions. The requisite stereochemistry at C12 and C13 were secured by desymmetric benzoylation and Roush allylation respectively. cis-THF ring was obtained via both osmate-mediated oxidative cyclization route and VO(acac)2-mediated epoxidation followed by acidic cyclization route with (Z)-alkene. Shi epoxidation with (E)-alkene followed by acidic cyclization and oxidative lactonization in Anelli’s conditioin furnished desired trans-THF and lactone with high diastereoselectivity. The right segment 85 was synthesized from desymmetric benzoylation of 2-methylpropane-1,2,3-triol over 26 steps in 15% overall yield via two different epoxidation route.The left segment (C1-C10) was synthesized via Evans aldol reaction and anti-aldol coupling. The reduction of β-hydroxy ketone to anti-alcohol was conducted successfully via Evans-Tishchenko method to give 222 as a major with a 26 : 1 d.r..The key intermediate 258 was obtained in high yield via Horner-Wadsworth-Emmons reaction of 85 and β-ketophosphonate 257 derived from 222.
Advisors
Lee, Hee-Seungresearcher이희승Kang, Sung-Ho강성호
Description
한국과학기술원 : 화학과,
Publisher
한국과학기술원
Issue Date
2014
Identifier
591885/325007  / 020087002
Language
eng
Description

학위논문(박사) - 한국과학기술원 : 화학과, 2014.8, [ vi, 88 p ]

Keywords

B-alkyl Suzuki-Miyaura coupling; Shi epoxidation; oxidative lactonization; Evans aldol reaction; Evans-Tishchenko reduction; 레이드로마이신; B-알킬 스즈키 커플링; 비대칭화 벤조일레이션; shi 에폭시화 반응; Evans-Tishchenko 환원; Evans 알돌; 산화성 락톤화 반응; Laidlomycin; Horner-Wadsworth-Emmons reaction

URI
http://hdl.handle.net/10203/196468
Link
http://library.kaist.ac.kr/search/detail/view.do?bibCtrlNo=591885&flag=dissertation
Appears in Collection
CH-Theses_Ph.D.(박사논문)
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