Introduction to chiral crystallization of achiral organic compoundsSpontaneous generation of chirality

Matsuura, Teruo; Koshima, Hideko

doi:10.1016/j.jphotochemrev.2005.02.002

Cited by 174 publications

(90 citation statements)

References 38 publications

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“…Chiral crystallization of achiral organic compounds has been one of the important candidates for the origin of chirality (Kahr and Gurney 2001;Sakamoto 1997;Matsuura and Koshima 2005;. Stereospecific reactions using enantiomorphous crystals as reactants in the solid state have been reported to form enantioenriched organic compounds (Penzien and Schmidt 1969;Green et al 1979;Claborn et al 2008).…”

Section: Introductionmentioning

confidence: 99%

Asymmetric Autocatalysis Induced by Chiral Crystals of Achiral Tetraphenylethylenes

Kawasaki

Nakaoda

Kaito

et al. 2009

Orig Life Evol Biosph

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The achiral hydrocarbon tetraphenylethylene crystallizes in enantiomorphous forms (chiral space group: P2(1)) to afford right- and left-handed hemihedral crystals, which can be recognized by solid-state circular dichroism spectroscopic analysis. Chiral organic crystals of tetraphenylethylene mediated enantioselective addition of diisopropylzinc to pyrimidine-5-carbaldehyde to give, in conjunction with asymmetric autocatalysis with amplification of chirality, almost enantiomerically pure (S)- and (R)-5-pyrimidyl alkanols whose absolute configurations were controlled efficiently by the crystalline chirality of the tetraphenylethylene substrate. Tetrakis(p-chlorophenyl)ethylene and tetrakis(p-bromophenyl)ethylene also show chirality in the crystalline state, which can also act as a chiral substrate and induce enantioselectivity of diisopropylzinc addition to pyrimidine-5-carbaldehyde in asymmetric autocatalysis to give enantiomerically enriched 5-pyrimidyl alkanols with the absolute configuration correlated with that of the chiral crystals. Highly enantioselective synthesis has been achieved using chiral crystals composed of achiral hydrocarbons, tetraphenylethylenes, as chiral inducers. This chemical system enables significant amplification of the amount of chirality using spontaneously formed chiral crystals of achiral organic compounds as the seed for the chirality of asymmetric autocatalysis.

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Section: Introductionmentioning

confidence: 99%

Asymmetric Autocatalysis Induced by Chiral Crystals of Achiral Tetraphenylethylenes

Kawasaki

Nakaoda

Kaito

et al. 2009

Orig Life Evol Biosph

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“…However, the chirality can have had origin also from many other processes which have been reviewed recently (Cataldo et al 2005); furthermore, a number of other photochemical events can generate the chirality (Matsuura and Koshima 2005;Inoue and Ramamurthy 2004).…”

Section: Introductionmentioning

confidence: 99%

γ-Radiation Induced Polymerization of a Chiral Monomer: A New Way to Produce Chiral Amplification

Cataldo

Brucato

Keheyan

2006

Orig Life Evol Biosph

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The treatment of the terpene beta(-)pinene with gamma radiation (at dose level: 150, 300 and 600 kGy) causes its polymerization into a resin and into a dimer. The yield of the resin and of the dimer appears to be linearly dependent to the radiation dose. The structure of the products was studied by FT-IR spectroscopy also in comparison to a reference beta(-)pinene resin prepared by cationic polymerization. A highly ordered structure was found in the case of the radiopolymer in comparison to the resin from cationic polymerization. Polarimetric measurements have shown astonishing enhancement in the optical activity of the radiopolymer and radiodimer in comparison to the starting optical activity of the beta(-)pinene monomer. Also DSC (differential scanning calorimetry) data supports the unexpected highly ordered structure for the beta(-)pinene radiopolymer in comparison to the resin prepared by cationic polymerization. The results have been discussed in terms of amplification of chirality caused by gamma radiation and the implications of this fact on the mechanism of chiral amplification on prebiotic molecules.

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“…The stochastic nature was nicely demonstrated in the crystallization of sodium chlorate [25] and amino acids glutamic acid and lysine [26]. Relevant results have been reviewed from several different aspects [27][28][29][30][31][32] and extended to phase transitions in general [33][34].…”

Section: Stochastic Experimental Observations Relevant For Chirality mentioning

confidence: 99%

The Role of Stochastic Models in Interpreting the Origins of Biological Chirality

Lente

2010

Symmetry

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This review summarizes recent stochastic modeling efforts in the theoretical research aimed at interpreting the origins of biological chirality. Stochastic kinetic models, especially those based on the continuous time discrete state approach, have great potential in modeling absolute asymmetric reactions, experimental examples of which have been reported in the past decade. An overview of the relevant mathematical background is given and several examples are presented to show how the significant numerical problems characteristic of the use of stochastic models can be overcome by non-trivial, but elementary algebra. In these stochastic models, a particulate view of matter is used rather than the concentration-based view of traditional chemical kinetics using continuous functions to describe the properties system. This has the advantage of giving adequate description of single-molecule events, which were probably important in the origin of biological chirality. The presented models can interpret and predict the random distribution of enantiomeric excess among repetitive experiments, which is the most striking feature of absolute asymmetric reactions. It is argued that the use of the stochastic kinetic approach should be much more widespread in the relevant literature.

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Introduction to chiral crystallization of achiral organic compoundsSpontaneous generation of chirality

Cited by 174 publications

References 38 publications

Asymmetric Autocatalysis Induced by Chiral Crystals of Achiral Tetraphenylethylenes

Asymmetric Autocatalysis Induced by Chiral Crystals of Achiral Tetraphenylethylenes

γ-Radiation Induced Polymerization of a Chiral Monomer: A New Way to Produce Chiral Amplification

The Role of Stochastic Models in Interpreting the Origins of Biological Chirality

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