4.6 Article

Cooperative Catalysis with Coupled Chiral Induction in 1,3-Dipolar Cycloadditions of Azomethine Ylides

期刊

CHEMISTRY-A EUROPEAN JOURNAL
卷 24, 期 32, 页码 8092-8097

出版社

WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201801433

关键词

asymmetric catalysis; cooperative catalysis; cycloadditions; density functional calculations; enantioselective synthesis

资金

  1. Spanish Ministerio de Economia y Competitividad (MINECO) [CTQ2013-43446-P, CTQ2014-51912-REDC]
  2. Spanish Ministerio de Economia, Industria y Competitividad, Agencia Estatal de Investigacion (AEI)
  3. Fondo Europeo de Desarrollo Regional (FEDER, EU) [CTQ2016-76782-P, CTQ2016-80375-P, CTQ2016-81797-REDC]
  4. Generalitat Valenciana [PROMETEOII/2014/017]
  5. Gobierno Vasco/ Eusko Jaurlaritza (GV/EJ) [IT673-13]
  6. University of Alicante
  7. JSPS [17H03060]

向作者/读者索取更多资源

1,3-Dipolar cycloadditions (1,3-DC) between imino esters (as precursors of N-metallated azomethine ylides) and -deficient alkenes are promoted by cooperative asymmetric Lewis acid/BrOnsted base catalysis. The components of these catalytic pairs are silver salts derived from enantiopure commercially available BINOL-based phosphoric acids and Cinchona alkaloids. Chiral phosphoric silver(I) salts promote HOMO raising of in situ formed 1,3-dipoles, whereas protonated cinchona alkaloids generate a LUMO lowering for the dipolarophiles resulting in a global acceleration of the 1,3-DC. The best results were obtained with BINOL-derived silver phosphate and hydrocinchonine. Matching between both cooperative metallo- and organocatalyst results in an enhanced enantiomeric excess, superior to that reached by both separate components. NOESY experiments and DFT calculations are compatible with a non-covalent interaction (hydrogen bond) between both catalysts, which results in close contacts and mutually coupled chiral environments.

作者

我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。

评论

主要评分

4.6
评分不足

次要评分

新颖性
-
重要性
-
科学严谨性
-
评价这篇论文

推荐

暂无数据
暂无数据