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Studies on the catalytic cyanosilylation of carbonyl compounds and synthesis of pyrroles and bicyclic chiral aminoalcohols

Title
Studies on the catalytic cyanosilylation of carbonyl compounds and synthesis of pyrroles and bicyclic chiral aminoalcohols
Authors
박보영
Issue Date
2010
Department/Major
대학원 화학·나노과학과
Publisher
이화여자대학교 대학원
Degree
Master
Advisors
이상기
Abstract
Three different topics are comprised in this thesis research: the first topic is the a dream combination for catalysis: highly reactive and recyclable scandium(Ⅲ) triflate-catalyzed cyanosilylations of carbonyl compounds in an ionic liquid, the second topic is tandem one-pot synthesis of substituted pyrroles by using the blaise reaction intermediate, and the last topic is synthesis of chiral bicyclic aminoalcohols. Part Ⅰ: The catalytic activity of lanthanide triflates, particularly scandium triflate, was increased dramatically when the solvent was changed from organic to an ionic liquid, [bmim][SbF_(6)], allowing the cyanosilylation of a variety of aldehydes and ketones with a turnover frequency up to 48 000 mol h^(-1) and a total turnover number of 100 000. Part Ⅱ: The tandem reaction of the Blaise reaction intermediates with propagylic compounds having leaving group (-OTs, -OMs, -Br) has been investigated for the regioselective synthesis of polysubstituted pyrroles via SN2 propargylation and 5-exo-dig cyclization. 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.;졸업 논문의 연구는 크게 3 가지의 다른 주제로 구성되어 있다: Part Ⅰ의 주제는 촉매반응을 위한 dream combination : 이온성 액체를 사용하여 높은 반응성을 가지고 재사용 가능한carbonyl compounds의 scandium(Ⅲ) triflate-catalyzed cyanosilylations에 관한 연구이고, Part Ⅱ는 Blaise reaction intermediate를 사용한 substituted pyrroles의 tandem one-pot 합성에 관한 내용이다. 마지막 Part Ⅲ의 주제는 키랄 bicyclic aminoalcohols를 합성한 것에 관한 내용이다. Part Ⅰ: [bmim][SbF_(6)]를 사용한 lanthanide triflates, 특히 scandium triflate의 촉매 효능은 48 000 mol h^(-1) 이상의 turnover frequency 와 100,000의 total turnover number를 가지면서 다양한 aldehydes와 ketones 의 cyanosilylation을 현격히 증가시킨다. Part Ⅱ : Blaise reaction intermediates와 leaving group (-OTs, -OMs, -Br)을 가진 propargylic compounds의 tandem reaction은 SN2 propargylation과 5-exo-dig cyclization을 통하여 polysubstituted pyrroles을 위치선택적으로 합성할 수 있었다. 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-ols을 합성하였고, 생성물의 입체화학은 X-ray 분석을 통해 확인하였다. 합성된 키랄 bicyclic aminoalcohols는 다양한 비대칭 촉매반응의 키랄 리간드 또는 유기분자촉매 등에 효과적으로 작용할 것으로 기대된다.
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