樟腦分子架構衍生之有機催化劑在不對稱Baylis-Hillman與Petasis-Type反應的探討

Camphor-Derived Organocatalysts Catalyzed Asymmetric Baylis-Hillman and Petasis-Type Reactions

周才詠(Tsai-Yung Chou)

指導教授 ： 陳焜銘

國立臺灣師範大學/理學院/化學系/碩士(2010年)

摘要

有機催化劑應用在不對稱Baylis-Hillman及Petasis-Type反應，是建立新立體化學中心碳-碳鍵產物有效合成方式，常應用於天然物或藥物分子合成。藉由有機催化劑進行不對稱反應，為最經濟且環保的不對稱合成方法。本篇論文利用新合成之雙樟腦尿素有機催化劑97、98及實驗室已合成的硫尿素有機催化劑100~104，以雙氫鍵的活化方式進行不對稱Baylis-Hillman反應。雖然沒有達到我們的預期，但希望未來新合成的催化劑97、98在催化其他反應有很好的結果。
另外；藉著含有雙羥基的(S)-BINOL催化劑115，以單氫鍵活化的方式，可有效地進行不對稱Petasis-Type之反應。藉由改變催化劑、反應條件，探討對產物鏡像選擇性的影響，篩選出以1.0當量的反式-2-苯基乙烯基硼酸、喹啉和2.0當量氯甲酸苄酯為起始物，在二氯甲烷為溶劑及-40 oC的條件下，添加20 mol%的催化劑催化反應，可得到最佳之產率為76%及鏡像超越值63% ee。

關鍵字

有機不對稱催化於Baylis-Hillman 及 Petasis-Type 反應之探討

並列摘要

Utilizing organocatalysts asymmetric Baylis-Hillman and Petasis-Type reactions is a powerful tool for the construction of the carbon-carbon bonds. It is useful in natural product and medicine synthesis. It is the most economical and the environmental protection in asymmetric synthesis. We have design and synthesis of novel class of bis-camphor containing urea organocatalysts 97-98 and also utilized organocatalysts 100-104 are available in our laboratory for this asymmetric transformation. These catalysts were achieved by hydrogen bonding to produce desird product with high stereoselectivity.
　　In addition, it shows excellent results in using contain double hydroxyl group (S)-BINOL catalyst 115 with single hydrogen bonding activation for asymmetrical Petasis-Type reaction. Because of the change catalyst, the reacted condition, discusses to the product with enantionselectivity influence. The reaction was carried out by using the trans-2-phenylvinylboronic acid (1.0 equiv) and quinoline as the starting materials in dichloromethane in the presence of catalyst 115 (20 mol%) and benzyl chloroformate (2.0 equiv). The chemical yields of the desired product is up to 76% and ee value can be up to 63% ee.

並列關鍵字

Asymmetric Baylis-Hillman and Petasis-Type Reactions

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