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研究了醋酸铑[Rh2(OAc)4]与手性磷酸共催化的芳基重氮乙酸酯对吲哚化合物的不对称C—H官能团化反应,通过对吲哚C—H官能团化反应质子转移机制的研究,提出了通过不对称质子化实现金属卡宾与吲哚的C—H不对称官能团化反应的新策略.通过吲哚C—H官能团化反应氘代实验证明,在金属卡宾对N-烷基吲哚的碳氢官能团化中,质子迁移是一个分子间的反应,需要借助一个“质子梭”试剂完成,因此通过应用“手性质子梭”催化的不对称质子化有望实现反应的对映选择控制.通过选用手性磷酸作为“手性质子梭”实现了吲哚C—H官能团化反应的不对称催化,重氮化合物在醋酸铑的催化下形成金属卡宾,金属卡宾与吲哚反应生成潜手性的离子对中间体,在催化剂量的手性磷酸存在下,质子迁移通过双功能的手性磷酸完成,通过手性磷酸对潜手性的离子对中间体的不对称质子化实现了反应的对映选择性控制.反应给出了优秀的产率(最高可达99%),良好到优秀的对映选择性(最高可达94%ee),且此反应对其他N-芳基和N-硅基吲哚也有良好的反应兼容性.
The asymmetric C-H functionalization of indole compounds with aryl diazoacetates co-catalyzed by rhodium acetate [Rh2 (OAc) 4] and chiral phosphoric acid was studied. The functional groups of protons Transfer mechanism, a new strategy for asymmetric C-H functionalization of metal carbenes and indoles by asymmetric protonation is proposed.The deuterium experiments of the functionalization of indole C-H prove that when the metal carbene is N In the hydrocarbon functionalization of alkylindoles, proton migration is an intermolecular reaction that needs to be performed with a “proton shuttle” reagent, thus asymmetric protonation catalyzed by the “chiral proton shuttle” Is expected to realize the enantioselective control of the reaction.The asymmetric catalysis of indole C-H functionalization was achieved by using chiral phosphate as the “chiral proton” and the diazonium compound formed metal carbene catalyzed by rhodium acetate , Metal carbenes reacted with indoles to generate latent chiral ion-pair intermediates. Proton migration was accomplished by bifunctional chiral phosphoric acid in the presence of a catalytic amount of chiral phosphoric acid, Asymmetric protonation of the body The reaction gives excellent yields (up to 99%), good to excellent enantioselectivities (up to 94% ee), and this reaction gives good yields for other N-aryl There is also good reaction compatibility with N-silylindole.