铑催化的乙烯基环丙烷和一氧化碳的[5+1]环加成反应:反应拓展,应用,和机理研究

在前期工作中，我们发展了一种普适性较强的合成六元碳环的铑催化的乙烯基环丙烷和一氧化碳参与的[5+1]环加成反应。为进一步拓展该[5+1]反应在合成化学上的应用，我们将研究和发展环丙烷化反应/[5+1]反应, [5+1]反应/Nazarov反应等来高效合成多环体系。为了提高[5+1]反应的效率, 我们还将研究用两亲性B-Rh催化剂来催化[5+1]反应，探索利用醛和醇作为[5+1]反应中新的CO来源的可行性。本基金还将发展一种去对称化的[5+1]反应, 以期提供一种不对称合成5/6 并环的新方法。为了进一步探讨[5+1]反应在有机合成上的优势和特点, 我们将开展利用[5+1]反应作为关键反应来合成天然产物Sinularianin B 和Lycopladine H。利用计算化学来探讨所研究的[5+1]反应的详细机理也是本次基金的研究重点之一。

Developing reactions to access six-membered carbocycles is very important in the science of synthesis. We previously developed a Rh-catalyzed [5+1] cycloaddition reaction of vinylcyclopropanes and CO for the synthesis of cyclohexenones. In this research proposal, we will continue our efforts to further develop this reaction so that it can be used to solve many other challenges in organic synthesis. We will study and develop cyclopropanation/[5+1] reaction, [5+1]/Nazarov reaction, [5+1]/Rautenstauch reaction for the synthesis of multicyclic skeletons. We will also investigate whether zwitterionic B-Rh catalyst can catalyze the [5+1] reaction or not. Using aldehydes or alcohols as the CO source for the Rh-catalyzed [5+1] reaction will be tested. In addition, desymmetrizing [5+1] reaction for asymmetric synthesis of bicyclic 5/6 skeletons, application of [5+1] reaction in total syntheses of Sinularianin B and Lycopladine H, as well as the reaction mechanism, regio- and stereo-chemistry of [5+1] reaction will also be investigated.