Transition-Metal-Catalyzed Tandem C-C Bond Formations
- Abstract
- ◁그림 삽입▷(원문을 참조하세요)
전이금속 촉매를 이용한 연속적인 C-C 결합 형성 반응은 간단한 물질로부터 복잡한 화합물을 만드는데 아주 효율적인 반응이고, 특히 고리 화합물을 만드는데 다양한 연속적인 결합 방법들이 적용되고 있다. 이 연구에서는 로듐(Ι) 촉매를 이용한 연속적인 콘쥬게이트 첨가반응과 Mannich 고리형성반응을 이용해 테트라하이드로퀴놀린을 만들 수 있었고, 다양한 치환기의 도입이 가능하였다.
이 반응은 연속적인 C-C 결합 형성 반응에서, 이민이 두번째 친전자체로써 작용하여 (oxa-π-allyl)rhodium(Ι) 중간체와 분자내 반응을 통해 고리가 형성되는 첫번째 예이다.
◁그림 삽입▷(원문을 참조하세요)
Transition-metal-catalyzed tandem C-C bond formations are powerful methods for the synthesis of structurally complex molecules from relatively simple starting materials in a convergent way. Treatment of imine-substituted electron-dificient alkenes with arylboronic acids in the presence of [Rh(OH)(cod)]₂ afforded the fully substituted tetrahydroquinolines via tandem conjugate addition and Mannich cyclization reaction. These reactions were performed with a variety of arylboronic acids and imine-substituted α,β-unsaturated esters to provide the corresponding tetrahydroquinoline derivatives. This process represents the first example in which an imine group can serve as a secondary electrophile that accepts the (oxa-π-allyl)rhodium(Ι) intermediate in an intramolecular way.
- Issued Date
- 2009
- Awarded Date
- 2009. 2
- Type
- Dissertation
- Publisher
- 부경대학교 대학원
- Alternative Author(s)
- 이호봉
- Affiliation
- 부경대학교 대학원
- Department
- 대학원 화학과
- Advisor
- 소원연
- Table Of Contents
- 1. Introduction = 1
2. Results and Discussion = 4
2.1. Rhodium-Catalyzed Tandem Conjugate Addition-Mannich Cyclization Reaction: Straightforward Access to Fully Substituted Tetrahydroquinolines = 4
2.2. Related Catalytic Tandem Annulation Reactions = 10
3. Conclusion = 16
4. Experiment Section = 17
4.1. General information = 17
4.2. General procedure for the preparation of N-Boc aniline Ⅰ = 17
4.3. General procedure for Heck reaction for the synthesis of Ⅱa-c^(14a) = 18
4.4. Synthesis of N-Boc-4-methyl-2-vinylaniline (Ⅱd)^(14b) = 18
4.5. General procedure for the N-Boc deprotection = 19
4.6. Synthesis of 3-(2-aminophenyl)acrylonitrile (Ⅲc)^(14a) = 19
4.7. General procedure for the preparation of imine substrates 1 = 19
4.8. Systematic screen = 23
4.9. General procedure for rhodium(Ⅰ)-catalyzed tandem conjugate addition-Mannich cyclization reaction of imine-substituted electron-deficient alkenes 1 with arylboronic acids = 24
4.10. General procedure for Heck reaction for the synthesis of 5 = 43
4.11. General procedure for Sonogashira reaction for the synthesis of Ⅵa = 44
4.12. General procedure for Sonogashira reaction for the synthesis of Ⅵb,c = 44
4.13. General procedure for Sonogashira reaction for the synthesis of Ⅷa,c,d = 45
4.14. General procedure for Sonogashira reaction for the synthesis of Ⅷb = 45
4.15. General procedure for the preparation of imine substrates 3, 7, 9 = 46
5. Reference = 47
6. Spectral Data = 50
7. Korean Abstract = 79
- Degree
- Master
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