Elaboration of a Chiral Aziridine: Asymmetric Synthesis of 3-(Hydroxymethyl)-1,2,3,4-tetrahydroisoquinolin-4-ols
- 주제(키워드) tetrahydroisoquinoline , aziridine , asymmetric synthesis
- 발행기관 서강대학교 일반대학원
- 지도교수 이원구
- 발행년도 2011
- 학위수여년월 2011. 2
- 학위명 석사
- 학과 및 전공 일반대학원 화학과
- 실제URI http://www.dcollection.net/handler/sogang/000000046385
- 저작권 서강대학교의 논문은 저작권 보호를 받습니다.
초록/요약
광학적으로 순수한 (S)-N-methoxy-N-methyl-1-[(R)-1-phenylethyl]aziridine-2-carboxamide 4 로부터 유도된 functionalized 3,4-dihydroisoquinolines 17 을 이용하는 것은 3-(hydroxymethyl)-1,2,3,4-tetrahydroisoquinolin-4-ols 19 을 합성하는 효과적인 방법이다. (1S,3S,4R)-4-(tert-butyldimethylsilyloxy)-3-[(tert-butyldimethylsilyloxy)methyl]-6,7-dimethoxy-1,2-disubstituted-1,2,3,4-tetrahydroisoquinolines 18 은 고리형 이민 17 의 입체선택적인 환원 반응으로 얻어지고 desilylation 반응을 통하여 광학적으로 순수한 (1S,3S,4R)-3-(hydroxymethyl)-6,7-dimethoxy-1,2-disubstituted-1,2,3,4-tetrahydroisoquinolin-4-ols 19 을 좋은 수율로 얻을 수 있다. 또한, Pd 촉매 하의 N-arylation 반응과 C-C 짝지음 반응을 통해 새로운 tetracyclic 3-(hydroxymethyl)-1,2,3,4-tetrahydroisoquinolin-4-ols 23, 25 의 비대칭적 합성을 성공하였다.
more초록/요약
Preparation of functionalized 3,4-dihydroisoquinolines 17 derived from (S)-N-methoxy-N-methyl-1-[(R)-1-phenylethyl]aziridine-2-carboxamide 4 is an effective route for the synthesis of 3-(hydroxymethyl)-1,2,3,4-tetrahydroisoquinolin-4-ols 19. Stereoselective reduction of the cyclic imines 17 resulted in (1S,3S,4R)-4-(tert-butyldimethylsilyloxy)-3-[(tert-butyldimethylsilyloxy)methyl]-6,7-dimethoxy-1,2-disubstituted-1,2,3,4-tetrahydroisoquinolines 18 and the desilylation of the TBS groups afforded (1S,3S,4R)-3-(hydroxymethyl)-6,7-dimethoxy-1,2-disubstituted-1,2,3,4-tetrahydroisoquinolin-4-ols 19 in good yield. Also, an asymmetric synthesis of novel tetracyclic 3-(hydroxymethyl)-1,2,3,4-tetrahydroisoquinolin-4-ols 23, 25 was successfully achieved via Pd-catalyzed N-arylation and C-C coupling reaction.
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