Definition
An absolute asymmetric chemical reaction is one induced by asymmetric physical conditions such as circularly polarized light (CPL) instead of by chemical reagents or catalysts. They can be divided into two categories: one is asymmetric synthesis and the other is asymmetric decomposition.
Overview
Asymmetric synthesis is driven by the introduction of chirality into an achiral system, a process known as asymmetric induction. One example of absolute asymmetric synthesis is the introduction of optical activity into helicenes (twisted polyaromatic hydrocarbons with six rings) studied by Kagan et al. (1974) in 1971, in which the optical yield was lower than 1 %. Enantiomeric enrichment of racemic compound such as amino acids by irradiation with circularly polarized light (CPL) is one of the well-known examples of asymmetric decomposition. The first experimental evidence of CPL-induced asymmetric decomposition was reported by Kuhn and Knopf (1930).
Various light sources such as...
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References and Further Reading
Bailey J, Chrysostomou A, Hough JH, Gledhill TM, MacCall A, Clark S, Menard F, Tamura M (1998) Circular polarization in star-formation regions: implications for biomolecular homochirality. Science 281:672–674
Bonner WA (2000) Parity violation and the evolution of biomolecular homochirality. Chirality 12:114–126
Bonner WA, Kavasmaneck PR, Martin FS (1974) Asymmetric adsorption of alanine by quartz. Science 186:143–144
Flores JJ, Bonner WA, Massey GA (1977) Asymmetric photolysis of (RS)-leucine with circularly polarized ultraviolet light. J Am Chem Soc 99:3622–3624
Goldanskii VI, Kuzmin VV (1989) Spontaneous breaking of mirror symmetry in nature and the origin of life. Sov Phys Usp 32:1–29, Asp Fiz Nauk 157:3–50
Kagan HB, Balavoine G, Moradpour A (1974) Can circularly polarized light be used to obtain chiral compounds of high optical purity? J Mol Evol 4:41–48
Kuhn W, Knopf E (1930) Darstellung optisch aktiver Stoffe mit Hilfe von Licht. Z Phys Chem Abteil B 7:292–310
Meierhenrich UJ, Nahon L, Alcaraz C, Bredehöft JH, Hoffmann SV, Barbier B, Brack A (2005) Asymmetric vacuum UV photolysis of the amino acid leucine in the solid state. Angew Chem Int Ed 44:5630–5634
Nishino H, Nakamura A, Inoue Y (2001) Synchronous enantiomeric enrichment of both reactant and product by absolute asymmetric synthesis using circularly polarized light. Part 1. Theoretical and experimental verification of the asymmetric photoisomerization of methyl norbornadiene-2-carboxylate to methyl quadricyclane-1-carboxylate. J Chem Soc Perkin Trans 2:1693–1700
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Nakagawa, K. (2014). Asymmetric Reaction, Absolute. In: Amils, R., et al. Encyclopedia of Astrobiology. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-27833-4_6-2
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DOI: https://doi.org/10.1007/978-3-642-27833-4_6-2
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Online ISBN: 978-3-642-27833-4
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Latest
Asymmetric Reaction, Absolute- Published:
- 09 February 2023
DOI: https://doi.org/10.1007/978-3-642-27833-4_6-3
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Asymmetric Reaction, Absolute- Published:
- 28 April 2015
DOI: https://doi.org/10.1007/978-3-642-27833-4_6-2