백금촉매를 이용한 수소화 조건에서의 탄소-탄소 결합형성에 관한 연구
Platinum(II)-catalyzed C-C bond formation under hydrogenation conditions
- 주제(키워드) 백금촉매 , 수소화반응 , reductive cyclization
- 발행기관 아주대학교
- 지도교수 장혜영
- 발행년도 2012
- 학위수여년월 2012. 2
- 학위명 박사
- 학과 및 전공 일반대학원 에너지시스템학부
- 실제URI http://www.dcollection.net/handler/ajou/000000012090
- 본문언어 한국어
- 저작권 아주대학교 논문은 저작권에 의해 보호받습니다.
초록/요약
Carbon-carbon bond forming reaction is one of key steps for the synthesis of natural products and pharmaceuticals. Synthesis of biologically active compounds involves many carbon-carbon bond forming processes, which should be efficient and ecological without forming large amounts of waste byproducts. Thus, development of atom economic, cost-effective, and environmentally benign C-C bond forming reaction is highly advantageous in the synthetic organic reaction. The use of hydrogen gas in catalytic reduction is one of the oldest and powerful catalytic methods. Therefore, catalytic hydrogenation has been extensively utilized in the industry and academia; however, the hydrogen-mediated C-C bond formation has been achieved only in the alkene hydroformylations and Fisher-Tropsch process by assistance of carbon monoxide. The expansion of the hydrogen-mediated reactions beyond simple reduction and Fisher-Tropsch process would be of a great importance to the organic synthesis. Herein, to develop hydrogen-mediated C-C bond formation, we hope to report platinum(II)-catalyzed C-C coupling of a variety using π-functional groups under hydrogenation conditions. The following chapters II and III discuss platinum-catalyzed hydrogenative coupling of activated alkene and alkyne-aldehydes. Platinum-catalyzed hydrogenative cyclizations of allene-π functional groups are described in chapter IV. Finally, we wish to introduce the first platinum-catalyzed cyclization of allyl halides-hydrazones in chapter V.
more목차
Part A. Platinum(II)-catalyzed C-C bond formation
under hydrogenation conditions
I. History of hydrogenative C-C bond formation
1. Introduction………………………………………………………3
2. References………………………………………………………9
II. Platinum-catalyzed hydrogen-mediated coupling of activated alkenes (bisenones)
1. Introduction……………………………………………………11
2. Results and discussion
A) Optimization…………………………………………………14
B) Examples of the substrate
i) Actvated alkene (bisenones) (intramolecular reaction) ………………………………………………17
ii) Unsucessful substates……………………………………19
C) Mechanism (deuterium labeling studies) ……………20
3. Conclusion……………………………………………………22
4. References……………………………………………………23
III. Platinum-catalyzed cyclization of alkyne-aldehydes.
1. Introduction……………………………………………………25
2. Results and discussion
A) Optimization…………………………………………………31
B) Examples of the substrate
i) Alkyne-aldehydes……………………………………………33
C) Mechanism …………………………………………………34
3. Conclusion……………………………………………………36
4. References……………………………………………………37
IV. Platinum-catalyzed hydrogenative cyclizations of allene-carbonyls, and allene-oximes.
1. Introrduction……………………………………………………39
2. Results and discussion
A) Optimization……………………………………………………45
B) Examples of cycloreduction
i) Allene-carbonyls, allene-oximes…………………………49
ii) Unsucessful substrates……………………………………50
C) Mechanism (deuterium labeling studies)………………50
3. Conclusion……………………………………………………53
4. References……………………………………………………54
V. Platinum-catalyzed cyclizations of allyl-halides and hydrazones under hydrogenation conditions.
1. Indroduction……………………………………………………59
2. Results and discussion
A) Optimaztion……………………………………………………63
B) Examples
i) Allyl-halides and hydrazones………………………………65
ii) Unsucessful substrates……………………………………67
C) Mechanism (deuterium labeling studies)………………68
3. Conclusion……………………………………………………74
4. References……………………………………………………75
Part B: Experimental section…………………………………78
II. Platinum-catalyzed hydrogen-mediated coupling of activated alkenes (bisenones)………………………………79
III. Platinum-catalyzed cyclization of alkyne-aldehydes…………………………………………………………82
IV. Platinum-catalyzed hydrogenative cyclizations of
allene-carbonyls, and allene-oximes………………………90
V. Platinum-catalyzed cyclizations of allyl-halides and hydrazones under hydrogenation conditions……………108
