Predictable Selectivity in Remote C−H Oxidation of Steroids: Analysis of Substrate Binding Mode
| Autor: | Miquel Costas, Giorgio Olivo, Giorgio Capocasa, Barbara Ticconi, Stefano Di Stefano, Osvaldo Lanzalunga |
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| Rok vydání: | 2020 |
| Předmět: |
010405 organic chemistry
Chemistry Supramolecular chemistry Substrate (chemistry) General Chemistry General Medicine 010402 general chemistry 01 natural sciences Combinatorial chemistry Catalysis 0104 chemical sciences Molecular recognition hydrogen bonds molecular recognition oxidation steroids supramolecular catalysis Reactivity (chemistry) Chirality (chemistry) Selectivity Supramolecular catalysis |
| Zdroj: | Angewandte Chemie. 132:12803-12808 |
| ISSN: | 1521-3757 0044-8249 |
| Popis: | Predictability is a key requirement to encompass late-stage C-H functionalization in synthetic routes. However, prediction (and control) of reaction selectivity is usually challenging, especially for complex substrate structures and elusive transformations such as remote C(sp3 )-H oxidation, as it requires distinguishing a specific C-H bond from many others with similar reactivity. Developed here is a strategy for predictable, remote C-H oxidation that entails substrate binding to a supramolecular Mn or Fe catalyst followed by elucidation of the conformation of the host-guest adduct by NMR analysis. These analyses indicate which remote C-H bonds are suitably oriented for the oxidation before carrying out the reaction, enabling prediction of site selectivity. This strategy was applied to late-stage C(sp3 )-H oxidation of amino-steroids at C15 (or C16) positions, with a selectivity tunable by modification of catalyst chirality and metal. |
| Databáze: | OpenAIRE |
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