Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 59, Issue 31, Pages 12703-12708Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202003078
Keywords
hydrogen bonds; molecular recognition; oxidation; steroids; supramolecular catalysis
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Funding
- MINECO of Spain [PGC2018-101737-B-I00, FJCI-2016-30243]
- Generalitat de Catalunya (ICREA Academia Award)
- Sapienza Universita di Roma [2018 RG1181641DCAAC4E]
- Generalitat de Catalunya [2017 SGR 00264]
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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(sp(3))-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(sp(3))-H oxidation of amino-steroids at C15 (or C16) positions, with a selectivity tunable by modification of catalyst chirality and metal.
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