A combined Raman optical activity and vibrational circular dichroism study on artemisinin-type products

Bogaerts, Jonathan; Desmet, Filip; Aerts, Roy; Bultinck, Patrick; Herrebout, Wouter A.; Johannessen, Christian

doi:10.1039/d0cp03257c

Cited by 26 publications

(33 citation statements)

References 37 publications

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“…A quantitative similarity analysis further confirms that the 60:40 ratio provides the best match with the experimental spectrum (cf. Supporting Information) [17] . The very good match of the population‐adjusted VCD spectrum can be seen as a reliable confirmation for an excess of the M ‐propeller.…”

Section: Methodsmentioning

confidence: 57%

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Chiral Molecular Propellers of Triarylborane Ammonia Adducts

2020

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Chiral molecular propeller conformations have been induced to various triaryl structures including trityl derivatives and triaryl boranes. For borane-amine adducts, such induced propeller chirality has not been reported yet due to the low energy barrier for racemization in typical triarylboranes such as B(C 6 H 5) 3 or B(C 6 F 5) 3. Herein we demonstrate that point-chirality in side chains of chiral triarylborane-ammonia adducts, that feature intramolecular hydrogen bonds in addition to the dative N→B bond, can efficiently be transferred to triarylborane propeller chirality. Employing X-ray crystallography and both electronic and vibrational circular dichroism (ECD/VCD) spectroscopy for structural characterizations, we investigate three examples with different steric demands of the incorporated chiral alkoxyl side groups. We elucidate the conformational preferences of the molecular propellers. Furthermore, we show that computationally predicted conformational preferences obtained for the isolated, only implicitly solvated molecules are actually opposite to the experimentally observed ones.

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Section: Methodsmentioning

confidence: 57%

“…Supporting Information). [17] The very good match of the population-adjusted VCD spectrum can be seen as a reliable confirmation for an excess of the M-propeller.…”

mentioning

confidence: 75%

Chiral Molecular Propellers of Triarylborane Ammonia Adducts

2020

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“…By measuring the difference in intensity between the two polarization states during the ROA experiment, information regarding the molecular absolute conguration (AC) and the conformation can be obtained. [1][2][3][4][5][6][7][8] One of the main applications of ROA is the empirical determination of the structural aspects of proteins, such as their secondary structure. [6][7][8] For small organic (bio)molecules (peptides, carbohydrates, natural products) the ROA spectra have proven to be substantially more difficult to interpret solely based on empirical data.…”

Section: Introductionmentioning

confidence: 99%

Paving the way to conformationally unravel complex glycopeptide antibiotics by means of Raman optical activity

et al. 2021

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“…Eine quantitative Ähnlichkeitsanalyse bestätigt ferner, dass ein 40:60‐Verhältnis die beste Übereinstimmung mit dem experimentellen Spektrum bietet (vgl. SI) [17] . Die sehr gute Übereinstimmung mit dem populationskorrigierten VCD‐Spektrum kann als eine zuverlässige Bestätigung für einen Überschuss des M ‐Propellers angesehen werden.…”

Section: Methodsunclassified

“…SI). [17] Die sehr gute Übereinstimmung mit dem populationskorrigierten VCD-Spektrum kann als eine zuverlässige Bestätigung für einen Überschuss des M-Propellers angesehen werden.…”

Section: Angewandte Chemieunclassified

Chirale molekulare Propeller basierend auf Triarylboran‐Ammoniak‐Addukten

2020

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Chirale molekulare Propellerkonformationen wurden bereits in verschiedenen Triarylstrukturen, einschließlich Tritylderivaten und Triarylboranen, induziert. Für Boran‐Amin‐Addukte wurde über eine solche induzierte Propellerchiralität bisher noch nicht berichtet, da die Racemisierungsbarrieren in typischen Triarylboranen wie B(C6H5)3 oder B(C6F5)3 zu niedrig sind. Hier wird gezeigt, dass Punktchiralität in den Seitenketten chiraler Triarylboran‐Ammoniak‐Addukte, die zusätzlich zur dativen N→B‐Bindung intramolekulare Wasserstoffbrücken aufweisen, effizient in eine Triarylboran‐Propellerchiralität übertragen werden kann. Unter Verwendung von Röntgenkristallographie und ECD/VCD‐Spektroskopie werden drei Beispiele mit unterschiedlichem sterischem Anspruch der chiralen Alkoxy‐Seitengruppen untersucht. Neben der Aufklärung der Konformationspräferenzen der molekularen Propeller wird gezeigt, dass rechnerisch vorhergesagte Konformationspräferenzen, die für die isolierten, nur implizit solvatisierten Moleküle erhalten wurden, den experimentell beobachteten entgegengesetzt sind.

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A combined Raman optical activity and vibrational circular dichroism study on artemisinin-type products

Abstract: Artemisinin and two of its derivatives, dihydroartemisinin and artesunate, which are front line drugs against malaria, were investigated using Raman optical activity (ROA) and vibrational circular dichroism (VCD) experiments, both...

Cited by 26 publications

References 37 publications

Chiral Molecular Propellers of Triarylborane Ammonia Adducts

Chiral Molecular Propellers of Triarylborane Ammonia Adducts

Paving the way to conformationally unravel complex glycopeptide antibiotics by means of Raman optical activity

Chirale molekulare Propeller basierend auf Triarylboran‐Ammoniak‐Addukten

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