Copper-Catalyzed Transfer Hydrodeuteration of Aryl Alkenes with Quantitative Isotopomer Purity Analysis by Molecular Rotational Resonance Spectroscopy
| Autor: | Isabella Y. Alansari, Justin L. Neill, Albert Reyes, Reilly E. Sonstrom, Zoua Pa Vang, Samantha E. Sloane, Martin Holdren, Joseph R. Clark, Brooks H. Pate |
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| Rok vydání: | 2021 |
| Předmět: |
chemistry.chemical_classification
Spectrometer Chemistry Alkene Analytical chemistry Regioselectivity General Chemistry Carbon-13 NMR 010402 general chemistry 01 natural sciences Biochemistry Catalysis 0104 chemical sciences Isotopomers Colloid and Surface Chemistry Deuterium Selectivity Spectroscopy |
| Zdroj: | Journal of the American Chemical Society. 143:7707-7718 |
| ISSN: | 1520-5126 0002-7863 |
| Popis: | A copper-catalyzed alkene transfer hydrodeuteration reaction that selectively incorporates one hydrogen and one deuterium atom across an aryl alkene is described. The transfer hydrodeuteration protocol is selective across a variety of internal and terminal alkenes and is also demonstrated on an alkene-containing complex natural product analog. Beyond using 1H, 2H, and 13C NMR analysis to measure reaction selectivity, six transfer hydrodeuteration products were analyzed by molecular rotational resonance (MRR) spectroscopy. The application of MRR spectroscopy to the analysis of isotopic impurities in deuteration chemistry is further explored through a measurement methodology that is compatible with high-throughput sample analysis. In the first step, the MRR spectroscopy signatures of all isotopic variants accessible in the reaction chemistry are analyzed using a broadband chirped-pulse Fourier transform microwave spectrometer. With the signatures in hand, measurement scripts are created to quantitatively analyze the sample composition using a commercial cavity enhanced MRR spectrometer. The sample consumption is below 10 mg with analysis times on the order of 10 min using this instrument-both representing order-of-magnitude reduction compared to broadband MRR spectroscopy. To date, these measurements represent the most precise spectroscopic determination of selectivity in a transfer hydrodeuteration reaction and confirm that product regioselectivity ratios of >140:1 are achievable under this mild protocol. |
| Databáze: | OpenAIRE |
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