Structure and Reactivity of N‐Heterocyclic Alkynyl Hypervalent Iodine Reagents
| Autor: | Jerome Waser, Rosario Scopelliti, Eliott Le Du, Elsa Anselmi, Matthew D. Wodrich, Thibaut Duhail, Emmanuel Magnier, Farzaneh Fadaei-Tirani |
|---|---|
| Přispěvatelé: | Ecole Polytechnique Fédérale de Lausanne (EPFL), Institut Lavoisier de Versailles (ILV), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANR-17-CE07-0048,HYPISUL,Iodosulfoximines hypervalentes comme agents de perfluoroalkylation(2017) |
| Jazyk: | angličtina |
| Rok vydání: | 2021 |
| Předmět: |
sulfoximine
010402 general chemistry 01 natural sciences Catalysis Amidine chemistry.chemical_compound alkynyl transfer Nucleophile Amide [CHIM]Chemical Sciences Reactivity (chemistry) Indole test chemistry.chemical_classification heterocycles Full Paper 010405 organic chemistry Chemistry Organic Chemistry Hypervalent molecule General Chemistry Full Papers Combinatorial chemistry 0104 chemical sciences Sulfonamide hypervalent iodine Reagent density functional calculations |
| Zdroj: | Chemistry (Weinheim an Der Bergstrasse, Germany) Chemistry-A European Journal Chemistry-A European Journal, Wiley-VCH Verlag, In press, ⟨10.1002/chem.202101475⟩ |
| ISSN: | 1521-3765 0947-6539 |
| Popis: | 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−Calkyne 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 σ‐hole regions for sulfonamide‐based compounds. Most reagents reacted well in the alkynylation of β‐ketoesters. The alkynylation of thiols afforded more variable yields, with compounds with a stronger σ‐hole reacting better. In metal‐mediated transformations, the N‐heterocyclic hypervalent iodine reagents gave inferior results when compared to the O‐based EBX reagents. Four new N‐heterocyclic alkynyl hypervalent iodine reagents have been synthesized. Their structures and reactivity are described and compared to already reported cyclic hypervalent iodine reagents, showing less extended σ holes for tosylated reagents. Good alkyne transfer properties towards strong nucleophiles were observed, but applications in radical and metal‐catalyzed processes were more limited. |
| Databáze: | OpenAIRE |
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