Tethered Counterion-Directed Catalysis: Merging the Chiral Ion-pairing and Bifunctional Ligand Strategies in Enantioselective Gold(I) Catalysis,Journal of the American Chemical Society

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Tethered Counterion-Directed Catalysis: Merging the Chiral Ion-pairing and Bifunctional Ligand Strategies in Enantioselective Gold(I) Catalysis
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2020-02-03 , DOI: 10.1021/jacs.9b11154
Zhenhao Zhang _{1,

2} , Vitalii Smal ₁ , Pascal Retailleau ₁ , Arnaud Voituriez ₁ , Gilles Frison ₂ , Angela Marinetti ₁ , Xavier Guinchard ₁

Affiliation

Tethering a metal complex to its phosphate counterion via a phosphine ligand enables a new strategy in Asymmetric Counteranion-Directed Catalysis (ACDC). A straightforward, scalable synthetic route gives access to the gold(I) complex of a chiral phosphine displaying a phos-phoric acid function. The complex generates a catalytically active species with an unprecedented intramolecular relationship between the cati-onic Au(I) center and the phosphate counterion. The benefits of tethering the two functions of the catalyst is demonstrated here in a tandem cycloisomerization/nucleophilic addition reaction, by attaining high enantioselectivity levels (up to 97% ee) at a remarkable low 0.2 mol% catalyst loading. Remarkably the method is also compatible with a silver-free protocol.

中文翻译：

系留反离子导向催化：在对映选择性金（I）催化中融合手性离子对和双功能配体策略

通过膦配体将金属络合物连接到其磷酸盐抗衡离子上，实现了不对称抗衡阴离子导向催化 (ACDC) 的新策略。一个简单的、可扩展的合成路线可以获得显示磷酸功能的手性膦的金 (I) 络合物。该复合物产生一种催化活性物质，在阳离子 Au(I) 中心和磷酸盐反离子之间具有前所未有的分子内关系。在串联环异构化/亲核加成反应中，通过在显着的 0.2 mol% 催化剂负载量下获得高对映选择性水平（高达 97% ee），证明了将催化剂的两种功能束缚在一起的好处。值得注意的是，该方法还与无银协议兼容。

更新日期：2020-02-03

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