New asymmetric syntheses utilizing (S)-2-indoline derivatives = 광학 활성을 갖는 인돌린 유도체를 이용한 비대칭 합성

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New chiral auxiliaries and catalysts have been synthesized from (S)-indoline-2-carboxylic acid and found to provide high stereoselectivities in various asymmetric reactions. Diastereoselective pinacol coupling reaction of the (-ketoamides in the presence of samarium (Ⅱ) diiodide gave the outstanding results of (S,S)-threo-pinacols up to > 99% de. The pinacol coupled diol (S-indoline-(S,S)-threo-pinacol) was hydrolyzed to (2S,3S)-dialkylsubstituted tartaric acid as the almost optically pure form ( > 99% de). S-2-Alkoxymethylindoline was recovered in ca. 90% yield. The absolute configuration was determined by X-ray crystallography and CD spectroscopy. While, octahydro (2S, 3aS, 7aS)-N-pyruvoyl-2-(t-butyldiphenylsilyloxy)-indoline, which was obtained by reduction of benzene ring of indoline to cyclohexane ring afforded the opposite configuration (R,R)-threo-pinacol (97% de). The absolute configuration of (R,R)-threo-pinacol (97% de) was determined by measuring [(]D of (S,S)-2,3-dimethyltartaric acid which was obtained from hydrolysis of (S,S)-threo-pinacol and by comparing it with the known one. It is the first to obtain optically pure 2,3-disubstituted tartaric acids. The asymmetric reductive homocoupling reaction at the 3-position of α,β-unsaturated amides with samarium (Ⅱ) diiodide which is a strong one electron donor resulted in 3,4-dialkyladipiamide derivatives with extremely high diastereoselectivities (up to > 99% de) with (3S,4S) configuration. The absolute configuration was determined by X-ray crystallography. The conjugate additions of dibenzyllithium amide to α,β-unsaturated amides of indoline derivatives proceeded rapidly to result in extremely high diastereoselectivities. The procedure can be readily carried out under atmospheric pressure, and the chiral auxiliary is recovered in high yield (up to 98 % de).
Advisors
Kim, Yong-Hae김용해
Description
한국과학기술원 : 화학과,
Publisher
한국과학기술원
Issue Date
2000
Identifier
157933/325007 / 000965062
Language
eng
Description

학위논문(박사) - 한국과학기술원 : 화학과, 2000.2, [ viii, 120 p. ]

Keywords

Samarium; Diasteroselectivity; Asymmetry synthesis; Chirality; 광학 활성; 사마리움; 입체 선택성; 비대칭 합성

URI
http://hdl.handle.net/10203/31522
Link
http://library.kaist.ac.kr/search/detail/view.do?bibCtrlNo=157933&flag=dissertation
Appears in Collection
CH-Theses_Ph.D.(박사논문)
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