Determination of the absolute structure of the chiral crystal consisting of achiral dibutylhydroxytoluene and asymmetric autocatalysis triggered by this chiral crystal

Matsumoto, Arimasa; Takeda, Sora; Harada, Shunya; Soai, Kenso

doi:10.1016/j.tetasy.2016.07.013

Cited by 7 publications

(3 citation statements)

References 71 publications

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“…In addition, chiral crystals composed of achiral Nbenzoylglycine, [44] 2-thenoylglycine, [45] cocrystals composed of two achiral compounds, [46] benzil, [47] tetraphenylethylene, [48] ethylenediammonium sulfate, [49] benzenecarboxylate, [50] and 2,6-di-tert-butyl-p-cresol (BHT) [51] are found to be chiral triggers of asymmetric autocatalysis (Scheme 6).…”

Section: Other Chiral Organic Crystalsmentioning

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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Section: Other Chiral Organic Crystalsmentioning

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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“…Enantiomorphous crystals formed from achiral N-benzoylglycine (hippuric acid) [96], 2-thenoylglycine [97], certain chiral cocrystals consisting of two achiral compounds [98], benzil [99], tetraphenylethylene [100], ethylenediammonium sulfate [101], aromatic triester [102], and 2,6-di-tert-butyl-p-cresol (BHT) [103] serve as chiral initiators of asymmetric autocatalysis (Scheme 7). It should be added that a chiral crystal composed of a racemic serine initiates asymmetric autocatalysis.…”

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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“…It was also found that enantiomorphous crystals composed of achiral N -benzoylglycine, 84) N -(2-thienylcarbonyl)glycine, 85) cocrystal of tryptamine and p -chlorobenzoic acid, 86) benzil, 87) tetraphenylethylene, 88) ethylenediamine sulfate, 89) benzene triester 90) and 2,6-di- t -butyl- p -cresol (BHT) 91) act as chiral triggers for asymmetric autocatalysis of 1c . Thus, asymmetric autocatalysis could serve as a macroscopic observation tool of molecular-level information on the structure of crystal surfaces.…”

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

confidence: 99%

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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Determination of the absolute structure of the chiral crystal consisting of achiral dibutylhydroxytoluene and asymmetric autocatalysis triggered by this chiral crystal

Cited by 7 publications

References 71 publications

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

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

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

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