Enantiodivergent formation of a chiral cytosine crystal by removal of crystal water from an achiral monohydrate crystal under reduced pressure

Mineki, Hiroko; Kaimori, Yoshiyasu; Kawasaki, Tsuneomi; Matsumoto, Arimasa; Soai, Kenso

doi:10.1016/j.tetasy.2013.09.020

Cited by 27 publications

(15 citation statements)

References 50 publications

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“…It was also found that dehydration of crystal water under reduced pressure, instead of heating, from the same enantiotopic face affords a chiral dehydrate cytosine crystal with the opposite chirality. 82) These results offer the first example of the formation of chiral crystals with controlled chirality by the dehydration of crystal water from an achiral crystal.…”

Section: Examination Of the Origins Of Chirality By Using Asymmetric mentioning

confidence: 79%

Asymmetric autocatalysis. Chiral symmetry breaking and the origins of homochirality of organic molecules

Soai

2019

Proceedings of the Japan Academy. Ser. B: Physical and Biologic

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Biological homochirality, such as that of l -amino acids, has been a puzzle with regards to the chemical origin of life. Asymmetric autocatalysis is a reaction in which a chiral product acts as an asymmetric catalyst to produce more of itself in the same absolute configuration. 5-Pyrimidyl alkanol was found to act as an asymmetric autocatalyst in the enantioselective addition of diisopropylzinc to pyrimidine-5-carbaldehyde. Asymmetric autocatalysis of 2-alkynyl-5-pyrimidyl alkanol with an extremely low enantiomeric excess of ca. 0.00005% exhibited significant asymmetric amplification to afford the same pyrimidyl alkanol with >99.5% enantiomeric excess and with an increase in the quantity of the same compound. We have employed asymmetric autocatalysis to examine the origin of homochirality. Asymmetric autocatalysis triggered by circularly polarized light, chiral minerals such as quartz, chiral organic crystals composed of achiral compounds gave highly enantioenriched pyrimidyl alkanol with absolute configurations corresponding with those of the chiral triggers. Absolute asymmetric synthesis without the intervention of any chiral factor was achieved. Chiral isotopomers acted as chiral triggers of asymmetric autocatalysis.

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Section: Examination Of the Origins Of Chirality By Using Asymmetric mentioning

confidence: 79%

Asymmetric autocatalysis. Chiral symmetry breaking and the origins of homochirality of organic molecules

Soai

2019

Proceedings of the Japan Academy. Ser. B: Physical and Biologic

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“…Elimination of water by heating from the opposite enantiotopic face of achiral cytosine monohydrate afforded chiral cytosine (anhydride) crystals with the opposite chirality [33] Interestingly, elimination of water from cytosine monohydrate crystals under reduced pressures at room temperature resulted in the formation of chiral cytosine (anhydride) crystals with the opposite chirality to that formed by heating. [34] These results are the first example to demonstrate that crystals with the controlled chirality are formed by eliminating crystal water from achiral crystals. Chiral cytosine crystals work as chiral triggers of asymmetric autocatalysis.…”

Section: Formation Of Chiral Cytosine Crystal By Enantiospecific Dehydration From Achiral Cytosine Monohydrate and Asymmetric Autocatalysmentioning

confidence: 79%

“…Cytosine crystal of CD(À )310(KBr) triggered the formation of (R)-pyrimidyl alkanol 1 c with high ee, while crystal of CD(+)310(KBr) gave (S)-pyrimidyl alkanol 1 c with high ee. [33,34]…”

Section: Formation Of Chiral Cytosine Crystal By Enantiospecific Dehydration From Achiral Cytosine Monohydrate and Asymmetric Autocatalysmentioning

confidence: 99%

Asymmetric Autocatalysis as a Link Between Crystal Chirality and Highly Enantioenriched Organic Compounds

Soai

Matsumoto

Kawasaki

2021

Israel Journal of Chemistry

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The origin of biological homochirality has attracted much attention. Pyrimidyl alkanols exhibit asymmetric autocatalysis with significant amplification of enantiomeric excess in the reaction between pyrimidine-5-carbaldehyde and diisopropyl zinc (the Soai reaction). Chiral inorganic crystals such as quartz, cinnabar and sodium chlorate act as chiral triggers of asymmetric autocatalysis to afford highly enantioenriched pyrimidyl alkanol, with the absolute configurations corresponding to those of the chiral crystals. Chiral organic crystals composed of achiral organic compounds such as cytosine, adenine dinitrate, and γ-glycine act as the chiral triggers of the Soai reaction to afford pyrimidyl alkanol with high ee that corresponds to the absolute configuration of the chiral trigger. This review describes that chiral minerals and chiral organic crystals act as the chiral triggers of the Soai reaction and that these chiral crystals are correlated to near-enantiopure chiral organic compounds.

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“…Interestingly, the chirality of the dehydrated crystal is determined by the enantiotopic face of the crystal from which the heating is applied. It is worth noting that the dehydration of the crystal water of cytosine monohydrate under reduced pressure conditions [94] also gives the chiral cytosine crystal with the opposite chirality to that dehydrated by heating. Thus, by removal of crystal water from an achiral crystal of cytosine monohydrate either by heating or under reduced pressure, the formation of chiral crystals with controlled absolute chirality was achieved.…”

Section: Chiral Crystals Formed From Achiral Organic Compoundsmentioning

confidence: 99%

Role of Asymmetric Autocatalysis in the Elucidation of Origins of Homochirality of Organic Compounds

2019

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Pyrimidyl alkanol and related compounds were found to be asymmetric autocatalysts in the enantioselective addition of diisopropylzinc to pyrimidine-5-carbaldehyde and related aldehydes. In the asymmetric autocatalysis with amplification of enantiomeric excess (ee), the very low ee (ca. 0.00005%) of 2-alkynyl-5-pyrimidyl alkanol was significantly amplified to >99.5% ee with an increase in the amount. By using asymmetric autocatalysis with amplification of ee, several origins of homochirality have been examined. Circularly polarized light, chiral quartz, and chiral crystals formed from achiral organic compounds such as glycine and carbon (13C/12C), nitrogen (15N/14N), oxygen (18O/16O), and hydrogen (D/H) chiral isotopomers were found to act as the origin of chirality in asymmetric autocatalysis. And the spontaneous absolute asymmetric synthesis was also realized without the intervention of any chiral factor.

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Enantiodivergent formation of a chiral cytosine crystal by removal of crystal water from an achiral monohydrate crystal under reduced pressure

Cited by 27 publications

References 50 publications

Asymmetric autocatalysis. Chiral symmetry breaking and the origins of homochirality of organic molecules

Asymmetric autocatalysis. Chiral symmetry breaking and the origins of homochirality of organic molecules

Asymmetric Autocatalysis as a Link Between Crystal Chirality and Highly Enantioenriched Organic Compounds

Role of Asymmetric Autocatalysis in the Elucidation of Origins of Homochirality of Organic Compounds

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