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dc.contributor.advisor이상기-
dc.contributor.author김주현-
dc.creator김주현-
dc.date.accessioned2016-08-25T04:08:00Z-
dc.date.available2016-08-25T04:08:00Z-
dc.date.issued2009-
dc.identifier.otherOAK-000000051725-
dc.identifier.urihttps://dspace.ewha.ac.kr/handle/2015.oak/177405-
dc.identifier.urihttp://dcollection.ewha.ac.kr/jsp/common/DcLoOrgPer.jsp?sItemId=000000051725-
dc.description.abstractThree different topics are comprised in this thesis research: Part I topic is the development of novel recoverable Ru-caomplexes for ring-closing metathesis, Part II topic is in situ activation of a latent Ru-complex by using ionic liquid, and the last topic is synthesis of chiral bicyclic aminoalcohols. Part Ι: Based on release-return metathesis mechanism, novel 2^(nd) generation Grubbs/Hoveyda-type catalysts have been designed and synthesized as a new-type of recoverable catalyst for ring-closing metathesis. In section 1, two different types of self-supported Grubbs/Hoveyda-type Ru-carbene complexes have been designed and synthesized, which catalyzed the ring-closing metathesis homogeneously, but recovered heterogeneously. In section 2, a new-type of Ru-carbene complexes tethering imidazolium tags at chelating isopropoxy groups has been synthesized. Through minor changes in the structure of imidazolium tag, as well as the composition of the ionic solvent system, highly reactive and recyclable Ru-complexes have been developed for RCMs in ionic liquid with minimal amounts of contamination of Ru residue in product. Part Ⅱ: A catalytically inactive Ru-carboxylate complex has been serendipitously isolated, and it can be in situ activated in ionic liquids (ILs) thermally. Addition of an equivalent amount of imidazolium halide and tetrabutyl ammonium halide further accelerated the ring-closing metathesis, which was largely dependent on ionic liquid anions, imidazolium halides and tetrabutylammonium halides. Part Ⅲ: Optically pure cis-fused 2-azabicyclo[3.3.0]octan-8-ols have been synthesized starting from commercially available racemic-cyclopenten-2-yl-acetic acid using (R)-α-methylbenzylamine as a sacrificial auxiliary. The absolute stereochemistry has been determined unambiguously by X-ray analysis. The synthesized chiral bicyclic aminoalcohols would be potentially useful in asymmetric catalysis as chiral ligands as well as organocatalysts.;졸업 논문의 연구는 크게 3가지의 다른 주제로 구성되어 있다: Part I의 주제는 ring-closing metathesis반응에 사용될 새로운 타입의 재사용이 가능한 Ru-촉매의 개발에 관한 연구이고, Part II는 이온성 액체를 사용하여 latent Ru-촉매를 in situ activation 시킨 것에 관한 내용이다. 마지막 Part Ⅲ 의 주제는 키랄 bicyclic aminoalcohols를 합성한 것에 관한 내용이다. Part Ι: Release-return 메커니즘에 근거하여 재사용이 가능한 새로운 타입의 2^(nd) generation Grubbs 촉매를 디자인하고 합성하였다. Section 1에서는 두 가지 타입의 self-supported Grubbs/Hoveyda-타입 Ru-carbene 촉매에 관해 연구하였다. 이들 촉매들은 ring-closing metathesis 반응 중에는 균일계 촉매로 작용하였고, 반응이 끝난 후에는 불균일계 회수가 가능하였다. Section 2에서는 isopropoxy 그룹에 imidazolium tag를 연결한 새로운 타입의 촉매를 합성하였다. Imidazolium tag의 구조와 용매 시스템의 조성에 약간의 변화를 주어 이온성 액체 내에서의 RCM 반응에 매우 뛰어난 반응성과 재 사용성을 보이는 Ru-촉매를 개발할 수 있었다. Part Ⅱ: 촉매반응에 비활성인 Ru-carboxylate 복합체를 이온성 액체 내에서 열에 의해 in situ activation 시켰다. 1당량의 imidazolium halide 와 tetrabutyl ammonium halide를 첨가하였을 때 ring-closing metathesis반응의 속도가 촉진되었고, 이온성 액체의 음이온과 imidazolium halide, tetrabutyl ammonium halide의 종류에 따라 반응성에 큰 차이를 보였다. Part Ⅲ: 출발물질은 라세믹 혼합물인 cyclopenten-2yl-acetic acid로, (R)-α-methylbenzylamine을 sacrificial auxiliary로 사용하여 광학적으로 순수한 cis-fused 2-azabicyclo[3.3.0]octan-8-ols 을 합성하였고, 생성물의 입체화학은X-ray 분석을 통해 확인하였다. 합성된 키랄 bicyclic aminoalcohols 는 다양한 비대칭 촉매반응의 키랄 리간드 또는 유기분자촉매 등에 효과적으로 작용할 것으로 기대된다.-
dc.description.tableofcontentsPartⅠ.Toward Development of Novel Recoverable Ru-Carbene Complexes for Ring-Closing Metathesis = 1 논문개요 = 2 Ⅰ-1.서론 = 3 Ⅰ-2.결과 및 고찰 = 13 <1>Section1 = 13 <1>-1.Self-supported catalyst Type A의 합성과 물성조사 = 13 <1>-2.Self-supported catalyst Type A의 반응성과 재 사용성 조사 = 18 <1>-3.Self-supported catalyst Type B의 합성과 NMR study = 21 <1>-4.Self-supported catalyst Type A의 반응성과 재사용 가능성 조사 = 23 <2>Section2 = 26 <2>-1.Ru-compex 29 의 합성 = 26 <2>-2.이온성 액체 층에서 catalyst 29a와 29b를 사용한 RCM반응 = 28 Ⅰ-3.결론 = 33 Ⅰ-4.실험(English) = 34 1.General methods = 34 <Section1-Type A> = 34 2.Synthesis of ruthenium complex 8 = 34 3.Synthesis of 9. = 37 4.Synthesis of 18. = 39 5.Synthesis of self-supported oligomeric Grubbs-Hoveyda Ru-carbene complexes 19. = 40 6.Ring-closing metathesis reactions = 41 <Section1-Type B> = 41 1.Synthesis of Ru-complex 22 = 41 2.Synthesis of polymeric Ru-carbene complex 23 via Ring-closing metathesis. = 43 <Section2> = 44 1.Synthesis of Ru-complex 29 = 44 2.A typical procedure for ring-closing metathesis in ionic liquid using catalysts 29. = 48 3.A typical procedure for cross metathesis 32 and 33 with methyl acrylate in [dmim][PF6]/toluene using catalyst 29b. = 49 PartⅡ.In situ activation of a latent Ru-carbene complex in ionic liquid = 67 논문개요 = 68 Ⅱ-1.서론 = 69 Ⅱ-2.결과 및 고찰 = 70 Ⅱ-3.결론 = 80 Ⅱ-4.실험 = 80 PartⅢ.Stereoselective synthesis of bicyclic chiral aminoalcohols for asymmetric catalysis = 99 논문개요 = 100 Ⅲ-1.서론 = 101 Ⅲ-2.결과 및 고찰 = 105 1.광학적으로 순수한 chiral auxiliary를 도입하여 bromo cyclization반응에서 diastereomeric mixture 5a, 5b를 분리 = 106 2.Key intermediate인 bicyclic amino ketone 10a의 합성과 absolute configuration의 결정 = 109 3.Nucleophilic addition과 hydride reduction을 통한 bicyclic amino alcohols시리즈의 합성 = 111 Ⅲ-3.결론 = 113 Ⅲ-4.실험 = 114 1.Synthesis of 3. = 114 2.Synthesis of 4. = 115 3.Synthesis of 5,6 = 116 4.Synthesis of 7a. = 117 7.Synthesis of 11. = 119 8.Synthesis of 12. = 120 9.Synthesis of 13. = 120 10.Synthesis of 14a. = 121 11.Synthesis of 15a. = 121 12.Synthesis of 7b. = 122 13.Synthesis of 8b. = 123 14.Synthesis of 9b. = 123 15.Synthesis of 10b. = 124 참고문헌 = 136 Abstract = 139-
dc.formatapplication/pdf-
dc.format.extent17522663 bytes-
dc.languagekor-
dc.publisher이화여자대학교 대학원-
dc.titleToward Development of Novel Recoverable Ru-Carbene Complexes for Ring-Closing Metathesis-
dc.typeMaster's Thesis-
dc.creator.othernameKim, Ju Hyun-
dc.format.pageⅷ, 140 p.-
dc.identifier.thesisdegreeMaster-
dc.identifier.major대학원 화학·나노과학과-
dc.date.awarded2009. 2-
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