Asymmetric Autocatalysis of Pyrimidyl Alkanol and Its Application to the Study on the Origin of Homochirality
Open accessAbstract
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 alcohols reveals a reversal of enantioselectivity in the addition of i-Pr2Zn to aldehyde and is one approach toward understanding the mechanism of asymmetric dialkylzinc addition, where heteroaggregates act as the catalytic species.
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Deracemization of conglomerates through Viedma ripening and asymmetric auto-catalysis with the Soai reaction have recently undergone significant progress.
“The topic has recently undergone significant progress thanks to numerous theoretical models and experimental validations, namely the deracemization of conglomerates through Viedma ripening 55 and the asymmetric auto-catalysis with the Soai reaction.56”
From Possible chemical and physical scenarios towards biological homochirality (2022) · cites this paper as [56]
The Soai reaction is an experimental validation of the Frank model.
“It is now wellrecognized that the Soai reaction, 56 an auto-catalytic asymmetric process (Fig. 12a), disclosed 42 years later, 310 is an experimental validation of the Frank model.”
From Possible chemical and physical scenarios towards biological homochirality (2022) · cites this paper as [56]
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- Authors
- Soai, K., Kawasaki, T., & Matsumoto, A.
- Affiliations
- Tokyo University of Science (JP)
- University of Fukui (JP)
- Venue
- Accounts of Chemical Research
- Publisher
- American Chemical Society (ACS)
- Published
- 2014-11-19
- Volume
- 47
- Issue
- 12
- Pages
- 3643-3654
- ISSN
- 0001-4842 (ISSN-L)
- 1520-4898
- OpenAlex
- W2040079916
- Cited by
- 181
- References
- 41
- Citations by year
- 2026: 5 · 2025: 11 · 2024: 7 · 2023: 13 · 2022: 25 · 2021: 11 · 2020: 15 · 2019: 22 · 2018: 12 · 2017: 22 · 2016: 26 · 2015: 12
- FWCI
- 10.78
- Type
- journal article
- Language
- en
- Open access
- hybrid
- doi.org
- Licence
- Locations
- Accounts of Chemical Research (publishedVersion, other-oa)
- PubMed (publishedVersion)
- Funders
- Japan Society for the Promotion of Science (NA)
- Ministry of Education, Culture, Sports, Science, and Technology (NA)
- Topics
- Physical Sciences › Physics and Astronomy › Astronomy and Astrophysics › Origins and Evolution of Life
- Physical Sciences › Chemistry › Organic Chemistry › Asymmetric Synthesis and Catalysis
- Physical Sciences › Chemistry › Organic Chemistry › Chemical Reaction Mechanisms
- Keywords
- asymmetric autocatalysis, origin of homochirality, enantiomeric excess amplification, diisopropylzinc, pyrimidine-5-carbaldehyde, chiral recognition, circularly polarized light, quartz, sodium chlorate, cinnabar, enantioselectivity
- MeSH terms
- Alcohols, Aldehydes, Catalysis, Pyrimidines, Stereoisomerism, Molecular Structure
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