The Pfeiffer effect with cinchoninium ion as a chiral environment substance

Miyoshi, Katsuhiko; Kuroda, Yasushige; Takeda, Junko; Yoneda, H.; Takagi, Ichiro

doi:10.1021/ic50196a003

Inorg. Chem.

1979

DOI: 10.1021/ic50196a003

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The Pfeiffer effect with cinchoninium ion as a chiral environment substance

Katsuhiko Miyoshi

Yasushige Kuroda

Junko Takeda

et al.

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Cited by 12 publications

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“…Apparently, the intermolecular interaction acts as the bridge for chirality transfer. [9] To evaluate the influence of the electrostatic interaction on the chirality of the POMs, we examined the CD spectral changes of (R,R)-BPEA-PMo 11 V with regard to the temperature and the solvent (Figure 1; see also Figure S6 in the Supporting Information). When the temperature was decreased from 40 to 0 8C, the intensity of the CD signal increased, which indicates that a high temperature is unfavorable for the induced chirality of the POMs.…”

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confidence: 99%

Chiral Heteropoly Blues and Controllable Switching of Achiral Polyoxometalate Clusters

Wang

et al. 2013

Angew Chem Int Ed

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confidence: 99%

Chiral Heteropoly Blues and Controllable Switching of Achiral Polyoxometalate Clusters

Wang

et al. 2013

Angew Chem Int Ed

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Chiral Heteropoly Blues and Controllable Switching of Achiral Polyoxometalate Clusters

Wang

et al. 2013

Angewandte Chemie

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Kinetic Control in the Chiral Recognition of Three‐Bladed Propellers

Bonnot

Aubert

Banerji

et al. 2010

Chemistry A European J

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The ion pair of the stereolabile C3‐symmetric, i+o proton complex [1⋅H]+ of diaza‐macropentacycle 1 and the configurationally stable Δ‐TRISPHAT ([Δ‐3]−) anion exists in the form of two diastereomers, namely, [Δ‐(1⋅H)][Δ‐3] and [Λ‐(1⋅H)][Δ‐3], the ratio of which, in terms of diastereomeric excess (de) decreases in the order [D8]THF (28 %)>CD2Cl2 (22 %)>CDCl3 (20 %)>[D8]toluene (16 %)>C6D6 (7 %)>[D6]acetone (0 %) at thermodynamic equilibrium. Except in the case of [D6]acetone, the latter is reached after a period of time that increases from 1 h ([D8]THF) to 24 h (CDCl3). Moreover, the initial value of the de of [1⋅H][Δ‐3] in CDCl3, before the thermodynamic equilibrium is reached, depends on the solvent in which the sample has been previously equilibrated (sample “history”). This property has been used to show that the crystals of [1⋅H][Δ‐3] formed by slow evaporation of CH2Cl2/CH3OH mixtures had 100 % de, which indicates that [1⋅H][Δ‐3] has enjoyed a crystallization‐induced asymmetric transformation. Structural studies in solution (NMR spectroscopy) and in the gas phase by calculations at the semiempirical PM6 level of theory suggest that the optically active anion is docked on the i+ (endo) external side of the proton complex such that one of the aromatic rings of [Δ‐3]− is inserted into a groove of [1⋅H]+, a second aromatic ring being placed astride the outside i+ pocket. Solvent polarity controls the thermodynamics of inversion of the [1⋅H]+ propeller. However, both polarity and basicity control its kinetics. Therefore, the rate‐limiting steps correspond to the ion‐pair separation/recombination and [1⋅H]+/1 deprotonation/protonation processes, rather than the inversion of [1⋅H]+, the latter being likely to take place in the deprotonated form (1).

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The Pfeiffer effect with cinchoninium ion as a chiral environment substance

Cited by 12 publications

References 12 publications

Chiral Heteropoly Blues and Controllable Switching of Achiral Polyoxometalate Clusters

Chiral Heteropoly Blues and Controllable Switching of Achiral Polyoxometalate Clusters

Chiral Heteropoly Blues and Controllable Switching of Achiral Polyoxometalate Clusters

Kinetic Control in the Chiral Recognition of Three‐Bladed Propellers

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