Sniffing out camphor: the fine balance between hydrogen bonding and London dispersion in the chirality recognition with α-fenchol

Quesada‐Moreno, María Mar; Fatima, Mariyam; Medel, Robert; Pérez, Cristóbal; Schnell, Melanie

doi:10.1039/d2cp00308b

Cited by 1 publication

(2 citation statements)

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“…This work has shown that CREST, a recently introduced tool for isomer searches in computational chemistry, successfully identifies low energy isomers of chiral tag complexes. This work supports the emerging consensus from the rotational spectroscopy community that CREST is a highly successful method for identifying the low‐energy isomers of weakly bound complexes 50,51,77–93 . Further, geometry optimization using dispersion corrected DFT gives chiral tag complex equilibrium geometries with sufficient accuracy to make a high‐confidence determination of the analyte absolute configuration.…”

Section: Discussionsupporting

confidence: 72%

“…This work supports the emerging consensus from the rotational spectroscopy community that CREST is a highly successful method for identifying the low-energy isomers of weakly bound complexes. 50,51,[77][78][79][80][81][82][83][84][85][86][87][88][89][90][91][92][93] Further, geometry optimization using dispersion corrected DFT gives chiral tag complex equilibrium geometries with sufficient accuracy to make a high-confidence determination of the analyte absolute configuration.…”

Section: Discussionmentioning

confidence: 99%

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Assignment of the absolute configuration of molecules that are chiral by virtue of deuterium substitution using chiral tag molecular rotational resonance spectroscopy

et al. 2023

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Chiral tag molecular rotational resonance (MRR) spectroscopy is used to assign the absolute configuration of molecules that are chiral by virtue of deuterium substitution. Interest in the improved performance of deuterated active pharmaceutical ingredients has led to the development of precision deuteration reactions. These reactions often generate enantioisotopomer reaction products that pose challenges for chiral analysis. Chiral tag rotational spectroscopy uses noncovalent derivatization of the enantioisotopomer to create the diastereomers of the 1:1 molecular complexes of the analyte and a small, chiral molecule. Assignment of the absolute configuration requires high‐confidence determinations of the structures of these weakly bound complexes. A general search method, CREST, is used to identify candidate geometries. Subsequent geometry optimization using dispersion corrected density functional theory gives equilibrium geometries with sufficient accuracy to identify the isomers of the chiral tag complexes produced in the pulsed jet expansion used to introduce the sample into the MRR spectrometer. Rotational constant scaling based on the fact that the diastereomers have the same equilibrium geometry gives accurate predictions allowing identification of the homochiral and heterochiral tag complexes and, therefore, assignment of absolute configuration. The method is successfully applied to three oxygenated substrates from enantioselective Cu‐catalyzed alkene transfer hydrodeuteration reaction chemistry.

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Section: Discussionsupporting

confidence: 72%

Section: Discussionmentioning

confidence: 99%

Assignment of the absolute configuration of molecules that are chiral by virtue of deuterium substitution using chiral tag molecular rotational resonance spectroscopy

et al. 2023

View full text Add to dashboard Cite

show abstract

Sniffing out camphor: the fine balance between hydrogen bonding and London dispersion in the chirality recognition with α-fenchol

Abstract: Binary complexes between the chiral monoterpenoids camphor and α-fenchol were explored with vibrational and rotational jet spectroscopy as well as density functional theory in order to explore how chirality can...

Cited by 1 publication

References 64 publications

Assignment of the absolute configuration of molecules that are chiral by virtue of deuterium substitution using chiral tag molecular rotational resonance spectroscopy

Assignment of the absolute configuration of molecules that are chiral by virtue of deuterium substitution using chiral tag molecular rotational resonance spectroscopy

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