Enantioselective formation of oxazolidinones from 2-substituted serinols = 2번 위치에 치환기를 가지는 세리놀로부터 광학활성을 가지는 옥사졸리디논의 형성에 관한 연구

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The chiral quarternary carbon with nitrogen atom is considered as valuable building blocks, which are found in various physiologically potent natural products, such as sphingofungin, lactacystin, salinosporamide A, kaitocephaline, lepardiformine etc. To the best of our knowledge, the methodologies of the enantioselective formation of t-alkylamines have been inefficient and rare. Recently, our group reported enantioselecive monobenzoylation of 2-substituted 2-benzamido-1,3-propanediols by catalytic desymmetrization to install quaternary carbon centers. Although this enantioselective monobenzoylation method was highly efficient in chemical yield and enantioselectivity, it had problems of practical use in organic synthesis. Herein, we report highly effective enantioselective formation of oxazolidinones from 2-substitued serinols via asymmetric tandem catalysis. The effective desymmetrization has been implemented using phenyl carbamate protected substrates with N,N-dimethyl benzylamine 127 in the presence of 5 mol% of the dimethyl phenyl bisoxazolidine (94)-CuCl2 complex in toluene at room temperature. Furthermore, subsequent asymmetric benzoylations via kinetic resolution in a pot enhance the enantioselectivity of the substrates in toluene and THF mixture. As a result, we reduced the amount of the chiral ligand copper complex from 20 mo% to 5 mol% in terms of the methodology. And we could get desired substrates with good chemical yields (70~89%) and excellent enantioselectivities (93~99% ee). In terms of practical organic synthesis, prepared benzoyl protected oxazolidinones are advantageous in further protections of the substrates to make unreactive for the other chemical reactions and deprotections to transform different functional groups.
Advisors
Kang, Sung-Horesearcher강성호
Description
한국과학기술원 : 화학과,
Publisher
한국과학기술원
Issue Date
2013
Identifier
513993/325007  / 020047346
Language
eng
Description

학위논문(박사) - 한국과학기술원 : 화학과, 2013.2, [ i, 70 p. ]

Keywords

Enantioselective; Oxazolidinones; 세리놀; 광학활성; 옥사졸리디논; 2-Substituted Serinols

URI
http://hdl.handle.net/10203/180289
Link
http://library.kaist.ac.kr/search/detail/view.do?bibCtrlNo=513993&flag=dissertation
Appears in Collection
CH-Theses_Ph.D.(박사논문)
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