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  4. Structure and Reactivity of N-Heterocyclic Alkynyl Hypervalent Iodine Reagents
 
research article

Structure and Reactivity of N-Heterocyclic Alkynyl Hypervalent Iodine Reagents

Le Du, Eliott  
•
Duhail, Thibaut
•
Wodrich, Matthew D.  
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June 4, 2021
Chemistry-A European Journal

Ethynylbenziodoxol(on)e (EBX) cyclic hypervalent iodine reagents have become popular reagents for the alkynylation of radicals and nucleophiles, but only offer limited possibilities for further structure and reactivity fine-tuning. Herein, the synthesis of new N-heterocyclic hypervalent iodine reagents with increased structural flexibility based on amide, amidine and sulfoximine scaffolds is reported. Solid-state structures of the reagents are reported and the analysis of the I-C-alkyne bond lengths allowed assessing the trans-effect of the different substituents. Molecular electrostatic potential (MEP) maps of the reagents, derived from DFT computations, revealed less pronounced sigma-hole regions for sulfonamide-based compounds. Most reagents reacted well in the alkynylation of beta-ketoesters. The alkynylation of thiols afforded more variable yields, with compounds with a stronger sigma-hole reacting better. In metal-mediated transformations, the N-heterocyclic hypervalent iodine reagents gave inferior results when compared to the O-based EBX reagents.

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CEJ2021-10979GoldAccess.pdf

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