Hydration of a Chiral Molecule: The Propylene Oxide⋅⋅⋅(Water)<sub>2</sub> Cluster in the Gas Phase

Su, Zheng; Xu, Yunjie

doi:10.1002/anie.200701966

Cited by 31 publications

(8 citation statements)

References 28 publications

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“…33 Quite interesting is the case of propylene oxide-(water) 2 trimer, where the addition of the second water as a proton donor switches the conformational stability of syn and anti propylene oxide-water dimer. 38…”

Section: Water As Proton Donor Producing An Inversion Of the Stabilit...mentioning

confidence: 99%

Internal dynamics in complexes of water with organic molecules. Details of the internal motions in tert-butylalcohol–water

Evangelisti

Camináti

2010

Phys. Chem. Chem. Phys.

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The peculiar propensity of water to have a high internal dynamic activity in its molecular complexes with organic molecules is described in this paper. Often, the corresponding large amplitude motions are reflected in the tunnelling splittings of the rotational transitions which, in turn, provide information for the determination of the potential energy surfaces and of the noncovalent interactions of water with a variety of atoms and/or functional groups. A classification of this kind of molecular complexes is given, also in relation to the tunnelling features of the rotational spectra. As a specific example, the rotational spectrum of tert-butylalcohol-water, investigated by Fourier transform microwave spectroscopy, is reported. Details are given of the large amplitude motions which take place in the adduct, the internal rotation of the hydroxyl group and the oscillations of the water molecule, by interpreting the experimental data with a flexible model.

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Section: Water As Proton Donor Producing An Inversion Of the Stabilit...mentioning

confidence: 99%

Internal dynamics in complexes of water with organic molecules. Details of the internal motions in tert-butylalcohol–water

Evangelisti

Camináti

2010

Phys. Chem. Chem. Phys.

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“…Water is one of the most heavily studied molecules on Earth, and its colligative structure and catalytic properties are still a subject of intense investigation. (29,30,31) Thus the means by which it affects selectivity in these cascades and organic reactions in general (32,33,34,35) is not without uncertainty at this point. Moreover, although the reactions appear to be homogeneous, we cannot rule out surface effects or the formation of micelles that impact the conformation and reactivity of the epoxy alcohols (5, 15, and 17).…”

Section: Mechanism and Implicationsmentioning

confidence: 99%

Epoxide-Opening Cascades Promoted by Water

Vilotijević

Jamison

2007

Science

267

178

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Selectivity rules in organic chemistry have been inferred largely from nonaqueous environments. In contrast, enzymes operate in water, and the chemical effect of the medium change remains only partially understood. Structural characterization of the "ladder" polyether marine natural products raised a puzzle that persisted for 20 years: Although the stereochemistry of adjacent tetrahydropyran (THP) cycles would seem to arise from a biosynthetic cascade of epoxide-opening reactions, experience in organic solvents argued consistently that such a pathway would be kinetically disfavored. We report that neutral water acts as an optimal promoter for the requisite ring-opening selectivity, once a single templating THP is appended to a chain of epoxides. This strategy offers a high-yielding route to the naturally occurring ladder core and highlights the likely importance of aqueous-medium effects in underpinning certain noteworthy enzymatic selectivities.

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“…Propylene oxide (PO) is a simple chiral molecule with a fairly rigid geometry, except for its methyl group internal rotation, and exists as a single conformer. This simplicity is one of the main reasons that PO has been widely used as a model chiral molecule in the development of theoretical treatments of chiroptical spectroscopies, such as vibrational circular dichroism, including its anharmonic treatment, [10–12] and in understanding solvent effects [13–15] . Not surprisingly, PO is also one of the earliest chiral molecules investigated using rotational spectroscopy [16,17] and the first chiral molecule detected in space, based on its rotational transitions [18] .…”

Section: Introductionmentioning

confidence: 99%

“…This simplicity is one of the main reasons that PO has been widely used as a model chiral molecule in the development of theoretical treatments of chiroptical spectroscopies, such as vibrational circular dichroism, including its anharmonic treatment, [10][11][12] and in understanding solvent effects. [13][14][15] Not surprisingly, PO is also one of the earliest chiral molecules investigated using rotational spectroscopy [16,17] and the first chiral molecule detected in space, based on its rotational transitions. [18] PO is known to bind to other molecules utilizing its ester oxygen atom, whereas its methyl group may serve as additional binding site or provides steric hindrance.…”

Section: Introductionmentioning

confidence: 99%

Conformational Landscape, Chirality Recognition and Chiral Analyses: Rotational Spectroscopy of Tetrahydro‐2‐Furoic Acid⋅⋅⋅Propylene Oxide Conformers

et al. 2021

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A chiral adduct formed between a chiral carboxylic acid, tetrahydro‐2‐furoic acid (THFA), and a chiral ester, propylene oxide (PO), was investigated using rotational spectroscopy and DFT calculations. Isolated THFA exists dominantly as three different conformers: I, II, and III in a jet, with I and II taking on the trans‐COOH configuration and III having the cis‐COOH configuration. We utilized CREST, a conformational ensemble space exploration tool, to identify the possible conformations of the binary adduct, THFA⋅⋅⋅PO. Subsequent DFT geometry optimizations predicted about two hundred homochiral and heterochiral binary structures with 28 low energy structures within an energy window of 15 kJ mol−1. A rich broadband rotational spectrum was obtained with a mixture of trace amounts of THFA+PO in neon in a supersonic jet expansion. Six THFA⋅⋅⋅PO conformers were identified experimentally. Kinetically favored binary products which contain trans‐COOH I dominate among the observed conformers, while thermodynamically more stable adducts were also detected. Detailed analyses of the structures of the observed conformers show interesting chirality‐controlled structural preferences. Such non‐covalently bound chiral contact pairs are the foundation of chiral‐tag rotational spectroscopy, an exciting new analytical application of rotational spectroscopy for determination of enantiomeric excess. Enantiomeric excess analyses were performed and the results are discussed.

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Hydration of a Chiral Molecule: The Propylene Oxide⋅⋅⋅(Water)₂ Cluster in the Gas Phase

Cited by 31 publications

References 28 publications

Internal dynamics in complexes of water with organic molecules. Details of the internal motions in tert-butylalcohol–water

Internal dynamics in complexes of water with organic molecules. Details of the internal motions in tert-butylalcohol–water

Epoxide-Opening Cascades Promoted by Water

Conformational Landscape, Chirality Recognition and Chiral Analyses: Rotational Spectroscopy of Tetrahydro‐2‐Furoic Acid⋅⋅⋅Propylene Oxide Conformers

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Hydration of a Chiral Molecule: The Propylene Oxide⋅⋅⋅(Water)2 Cluster in the Gas Phase

Cited by 31 publications

References 28 publications

Internal dynamics in complexes of water with organic molecules. Details of the internal motions in tert-butylalcohol–water

Internal dynamics in complexes of water with organic molecules. Details of the internal motions in tert-butylalcohol–water

Epoxide-Opening Cascades Promoted by Water

Conformational Landscape, Chirality Recognition and Chiral Analyses: Rotational Spectroscopy of Tetrahydro‐2‐Furoic Acid⋅⋅⋅Propylene Oxide Conformers

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Hydration of a Chiral Molecule: The Propylene Oxide⋅⋅⋅(Water)₂ Cluster in the Gas Phase