Herein, we present the synthesis of chiral triazole-based diaryliodonium salts and their application as monodentate asymmetric iodine(III) derivates in halogen bond (XB) catalyzed reactions. These potential Lewis acids were successfully benchmarked in the vinylogous Mannich reaction of cyanomethyl coumarin with isatin-derived ketimine to obtain the addition product in up to 99% yield and >99:1 e.r. Furthermore, these halogen bond catalysts allowed an efficient functionalization of ketimines with various alcohols toward N,O-acetals in up to 99% yield and 90:10 e.r. Additionally, we studied the origin of the enantioselectivity based on density functional theory (DFT) and the catalyst crystal structure. These unveiled an approach of asymmetric induction facilitated by using σ-hole stabilized chiral moieties in iodine(III)-based catalysts, predominantly predicated upon XB activation.

中文翻译：

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对映选择性卤素键催化中的手性三唑取代碘盐


在本文中，我们介绍了基于手性三唑的二芳基二芳基铵盐的合成及其在卤素键 （XB） 催化反应中作为单齿不对称碘 （III） 衍生物的应用。这些潜在的路易斯酸在氰甲基香豆素与菖丁衍生的酮的乙烯基曼尼反应中成功进行了基准测试，以高达 99% 的产率和 >99：1 e.r. 获得加成产物。此外，这些卤素键催化剂允许酮胺与各种醇以高达 99% 的产率和 90：10 的 e.r. 高效官能化为 N，O-缩醛。此外，我们基于密度泛函理论 （DFT） 和催化剂晶体结构研究了对映选择性的起源。这些揭示了一种不对称诱导方法，该方法通过在碘 （III） 基催化剂中使用 σ 孔稳定的手性部分来实现，主要基于 XB 活化。