Asymmetric syntheses using new chiral indoline derivatives = 광학활성을 갖는 새로운 인돌린 유도체들을 이용한 입체선택적 유기반응

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The new chiral auxiliaries for the stereoselective reactions were synthesized from (S)-indoline-2-carboxylic acid. These derivatives provided high stereo-selectivities in various asymmetric reactions. Diastereoselective addition of organometal reagents to new chiral a-ketoamides having (S)-2-methoxy-methylindoline resulted in a-hydroxyamides with extremely high diastereo-selectivities (up to 99% de). The reactions of organolithiums with chiral hydrazones derived from (S)-indoline-2-carboxylic acid afforded chiral hydrazines with high diastere-oselectivity (up to 99% de). As an application of the present method, (-)-coniine natural product was synthesized in high optical purity (94% ee). Diasteroselective addition of trimethylsilylcyanide to aldehyde (S)-1-amino-2-methoxymethyl-indoline hydrazones at -78℃ in $CH_2Cl_2$ in the presence of diethylaluminium- chloride gave chiral α-hydrazinonitriles in high optical yields (up to 96% de). During the course of sturdy on the cleavage of N-N bond of chiral hydrazines it has been found that α-hydrazinonitriles were smoothly dehydrogenated with palladium charcoal catalyst under mild conditions in the presence of cyclopentene to hydrazonoyl cyanides in good yields. Diastereoselective addition of aryllithium to chiral trifluoropyruvic aldehyde hydrazones gave the corresponding tertiary alcohols in good optical yield (up to 72% de), which may be used for the enantio-selective synthesis of Mosher reagent ((S) or (R)-α-methoxy-α-(trifluoro-methyl) phenyl acetic acid).
Advisors
Kim, Yong-Hae김용해
Description
한국과학기술원 : 화학과,
Publisher
한국과학기술원
Issue Date
1997
Identifier
112614/325007 / 000945459
Language
eng
Description

학위논문(박사) - 한국과학기술원 : 화학과, 1997.2, [ xii, 167 p. ]

Keywords

Asymmetric syntheses; Chiral auxiliary; 키랄 보조기; 비대칭 합성

URI
http://hdl.handle.net/10203/31460
Link
http://library.kaist.ac.kr/search/detail/view.do?bibCtrlNo=112614&flag=dissertation
Appears in Collection
CH-Theses_Ph.D.(박사논문)
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