Chiral Triazole-Substituted Iodonium Salts in Enantioselective Halogen Bond Catalysis
Year: 2024
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide 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.
Source: ACS Catalysis
Authors: Mattis Damrath, Tarek Scheele, Daniel Duvinage, Tim Neudecker, Boris J. Nachtsheim
Institution: University of Bremen
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
Funder: Deutsche Forschungsgemeinschaft
OpenAlex ID: W4405516340