Asymmetric Autocatalysis Induced by Cinnabar: Observation of the Enantioselective Adsorption of a 5‐Pyrimidyl Alkanol on the Crystal Surface

Shindo, Hitoshi; Shirota, Yusuke; Niki, Kaori; Kawasaki, Tsuneomi; Suzuki, Kenta; Araki, Yuko; Matsumoto, Arimasa; Soai, Kenso

doi:10.1002/ange.201304284

Cited by 14 publications

(4 citation statements)

References 52 publications

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“…70 Cinnabar, a chiral mineral of mercury(II) sulfide, mediates asymmetric autocatalysis. 71 Enantiomorphic P and M crystals of cinnabar act as chirality triggers for asymmetric autocatalysis to afford enantiomers (R)-and (S)-1, respectively. These results clearly show that chiral inorganic crystals trigger asymmetric autocatalysis, and the induced enantioimbalance is amplified efficiently to a high level by subsequent asymmetric autocatalysis.…”

Section: Enantioselective Synthesis Induced By Chiral Inorganic Crystalsmentioning

confidence: 99%

Asymmetric Autocatalysis of Pyrimidyl Alkanol and Its Application to the Study on the Origin of Homochirality

Soai¹,

Kawasaki

Matsumoto³

2014

Acc. Chem. Res.

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157

103

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CONSPECTUS: Amplification of enantiomeric excess (ee) is a key feature for the chemical evolution of biological homochirality from the origin of chirality. We describe the amplification of ee in the asymmetric autocatalysis of 5-pyrimidyl alkanols in the reaction between diisopropylzinc (i-Pr2Zn) and pyrimidine-5-carbaldehydes. During the reaction, an extremely low ee (ca. 0.00005% ee) can be amplified to >99.5% ee, and therefore, the initial slightly major enantiomer is automultiplied by a factor of ca. 630000, while the initial slightly minor enantiomer is automultiplied by a factor of less than 1000. In addition, pyrimidyl alkanols with various substituents at the 2-position of the pyrimidine ring, 3-quinolyl alkanol, 5-carbamoyl-3-pyridyl alkanol, and large multifunctionalized pyrimidyl alkanols also act as highly efficient asymmetric autocatalysts in the addition of i-Pr2Zn to the corresponding aldehydes. The asymmetric autocatalysis of pyrimidyl alkanol can discriminate the chirality of various compounds. Chiral substances such as alcohols, amino acids, hydrocarbons, metal complexes, and heterogeneous chiral materials can act as chiral triggers for asymmetric autocatalysis to afford pyrimidyl alkanols with the corresponding absolute configuration of the initiator. This recognition ability of chiral compounds is extremely high, and chiral discrimination of a cryptochiral quaternary saturated hydrocarbon was established by applying asymmetric autocatalysis. By using the large amplification effect of the asymmetric autocatalysis, we can link various proposed origins of chirality with highly enantioenriched organic compounds in conjunction with asymmetric autocatalysis. Thus, a statistical fluctuation in ee of racemic compounds can be amplified to high ee by using asymmetric autocatalysis. Enantiomeric imbalance induced by irradiation of circularly polarized light can affect the enantioselectivity of asymmetric autocatalysis. The asymmetric autocatalysis was also triggered by the morphology of inorganic chiral crystals such as quartz, sodium chlorate, and cinnabar. Chiral organic crystals of achiral compounds also act as chiral initiators, and during the study of a crystal of cytosine, enantioselective chiral crystal phase transformation of the cytosine crystal was achieved by removal of the water of crystallization in an achiral monohydrate crystal. Enantioselective C-C bond formation was realized on the surfaces of achiral single crystals based on the oriented prochirality of achiral aldehydes. Furthermore, asymmetric autocatalysis of pyrimidyl alkanols is a highly sensitive reaction that can recognize and amplify the significantly small effect of a chiral compound arising solely from isotope substitution of hydrogen, carbon, and oxygen (D/H, (13)C/(12)C, and (18)O/(16)O). These examples show that asymmetric autocatalysis with an amplification of chirality is a powerful tool for correlating the origin of chirality with highly enantioenriched organic compounds. Asymmetric autocatalysis using two β-amino alcoho...

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Section: Enantioselective Synthesis Induced By Chiral Inorganic Crystalsmentioning

confidence: 99%

Asymmetric Autocatalysis of Pyrimidyl Alkanol and Its Application to the Study on the Origin of Homochirality

Soai¹,

Kawasaki

Matsumoto³

2014

Acc. Chem. Res.

Self Cite

157

103

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“…The high density of the material's chiral binding sites is preserved even after grinding, thus overcoming the limitation traditionally associated with the use of flat chiral surfaces. 85 As already anticipated, several intermetallic compounds also have chiral bulk crystal structures. However, only a very recent work by Prinz reports the remarkable enantioselectivity of a prochiral molecule (9-etynylphenanthrene) on PdGa (P2 1 3) at room temperature.…”

Section: Enantioselectivitymentioning

confidence: 96%

Chirality in metals: An asymmetrical journey among advanced functional materials

Riva

2017

Materials Science and Technology

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Chirality is a property of matter which manifests at any length scale and can equally appear as quantum phenomena and in three-dimensional macroscopic structures. However, while chirality can be easily achieved by removing the inversion symmetry operation in hexagonal or tetragonal metal structures, chirality in metals is an unusual and barely developed phenomenon. Nevertheless, chirality can greatly alter mechanical and functional features of materials, making them suitable for catalysis, optics, electromagnetism, thermoelectricity and superconductivity; properties strictly dependent on the anisotropy of the crystal and on the direction of the applied force. This review aims to extend the definition of chirality to describe nanoclusters, metal surfaces and crystals and to provide an interdisciplinary overview on how symmetry can affect their properties.

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“…Chirality occurs commonly in organic and biological molecules/compounds [7][8][9][10] . Nevertheless, inorganic chiral entities possess distinctive characteristics such as the facile control of crystal structures and the tolerance to high-temperature stresses, which exhibit great promise for applications in chiral sensing [11][12][13] , advanced optical devices [14][15][16][17][18][19][20][21] , and asymmetric catalysis [22][23][24][25] .…”

Section: Introductionmentioning

confidence: 99%

Chirality Affecting Reaction Dynamics of HgS Nanostructures Simultaneously Visualized in Real and Reciprocal Space

Cao

Liu

et al. 2021

Preprint

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Chirality involved reactions enable to probe features in the fields of asymmetric synthesis and catalysis, which allow to gain insight into the fundamental mechanisms of topochemically controlled reactions. However, in situ observation of the chirality-associated reaction dynamics with simultaneous structural determination of new features has been lacking. Here, we report the direct visualization of the electron-beam-stimulated reaction dynamics of HgS nanostructures with chiral and achiral morphologies simultaneously in both real and reciprocal space. Under the electron-beam excitation of HgS nanostructures, the formation and evaporation dynamics of Hg nanodroplets were vividly pictured while the reciprocal space imaging revealed the structural transformation from monocrystalline to polycrystalline. Such induced changes were size-dependent, which were slowed down when involving the chirality in the nanostructures. The finding offers a fundamental understanding of topochemically controlled reaction mechanisms and holds promise of tuning asymmetric synthesis for catalysis related applications.

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Asymmetric Autocatalysis Induced by Cinnabar: Observation of the Enantioselective Adsorption of a 5‐Pyrimidyl Alkanol on the Crystal Surface

Cited by 14 publications

References 52 publications

Asymmetric Autocatalysis of Pyrimidyl Alkanol and Its Application to the Study on the Origin of Homochirality

Asymmetric Autocatalysis of Pyrimidyl Alkanol and Its Application to the Study on the Origin of Homochirality

Chirality in metals: An asymmetrical journey among advanced functional materials

Chirality Affecting Reaction Dynamics of HgS Nanostructures Simultaneously Visualized in Real and Reciprocal Space

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