Enantioselective Synthesis without Discrete Optically Active Additives
Abstract
By an adaptation of the asymmetric autocatalysis reactions of Soai, it was found that small enantiomeric excesses may be amplified to an arbitrary extent. When this process was applied 48 times to reactions in the absence of discrete optically active additives, all ultimately afforded substantial optical activity in the product. However, observations strongly suggest that most (and likely all) of these reactions are not true examples of absolute asymmetric synthesis. Rather, the ultimate optical activity arises from optically active impurities. Trace amounts of optically active materials may dominate the outcome of reactions involving asymmetric autocatalysis, and in the presence of opposite chiral influences a single enantiomer tends to take over a reaction. The possible implications of these observations to the origin of biological homochirality are noted.
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The outcome of the Soai reaction in absence of detectable chiral species is stochastic.
“In addition, the apparent outcome of the Soai reaction performed in the absence of detectable chiral species is stochastic as expected for a truly SMSB process”
From Possible chemical and physical scenarios towards biological homochirality (2022) · cites this paper as [332]
Cites
Asymmetric autocatalysis and amplification of enantiomeric excess of a chiral molecule
Soai, K., Shibata, T., Morioka, H., & Choji, K. (1995) · Nature · doi:10.1038/378767a0 · Cited by 1,085 · see citing works
Was photoresolution of amino acids the origin of optical activity in life?
NORDEN, B. (1977) · Nature · doi:10.1038/266567a0 · Cited by 108 · see citing works
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Absolute Asymmetric Synthesis: A Commentary
Mislow, K. (2003) · Collection of Czechoslovak Chemical Communications · doi:10.1135/cccc20030849 · Cited by 286 · see citing works
Crystalline Architectures as Templates of Relevance to the Origins of Homochirality
Weissbuch, I., & Lahav, M. (2011) · Chemical Reviews · doi:10.1021/cr1002479 · Cited by 284 · see citing works
Soai, K., Sato, I., Shibata, T., Komiya, S., Hayashi, M., Matsueda, Y., Imamura, H., Hayase, T., Morioka, H., Tabira, H., et al. (2003) · Tetrahedron: Asymmetry · doi:10.1016/s0957-4166(02)00791-7 · Cited by 266 · see citing works
Sato, I., Urabe, H., Ishiguro, S., Shibata, T., & Soai, K. (2003) · Angewandte Chemie International Edition · doi:10.1002/anie.200390105 · Cited by 232 · see citing works
Buhse, T., Cruz, J.-M., Noble-Terán, M. E., Hochberg, D., Ribó, J. M., Crusats, J., & Micheau, J.-C. (2021) · Chemical Reviews · doi:10.1021/acs.chemrev.0c00819 · Cited by 189 · see citing works
Phenomenon of Optical Self-Purification of Chiral Non-Racemic Compounds
Soloshonok, V. A., Ueki, H., Yasumoto, M., Mekala, S., Hirschi, J. S., & Singleton, D. A. (2007) · Journal of the American Chemical Society · doi:10.1021/ja065603a · Cited by 187 · see citing works
Self-citationPossible chemical and physical scenarios towards biological homochirality
Sallembien, Q., Bouteiller, L., Crassous, J., & Raynal, M. (2022) · Chemical Society Reviews · doi:10.1039/d1cs01179k · Cited by 186 · see citing works
Gridnev, I. D., Serafimov, J. M., Quiney, H., & Brown, J. M. (2003) · Organic & Biomolecular Chemistry · doi:10.1039/b307382n · Cited by 140 · see citing works
Singleton, D. A., & Vo, L. K. (2003) · Organic Letters · doi:10.1021/ol035605p · Cited by 130 · see citing works
Self-citationHighly enantioselective synthesis of organic compound using right- and left-handed helical silica
Sato, I., Kadowaki, K., Urabe, H., Jung, J. H., Ono, Y., Shinkai, S., & Soai, K. (2003) · Tetrahedron Letters · doi:10.1016/s0040-4039(02)02707-7 · Cited by 123 · see citing works
<i>Colloquium</i>: Homochirality: Symmetry breaking in systems driven far from equilibrium
Saito, Y., & Hyuga, H. (2013) · Reviews of Modern Physics · doi:10.1103/revmodphys.85.603 · Cited by 109 · see citing works
Schiaffino, L., & Ercolani, G. (2008) · Angewandte Chemie International Edition · doi:10.1002/anie.200802450 · Cited by 100 · see citing works
Viedma, C. (2007) · Crystal Growth & Design · doi:10.1021/cg060698d · Cited by 100 · see citing works
Demonstration of spontaneous chiral symmetry breaking in asymmetric Mannich and Aldol reactions
Mauksch, M., Tsogoeva, S. B., Wei, S., & Martynova, I. M. (2007) · Chirality · doi:10.1002/chir.20474 · Cited by 89 · see citing works
Ercolani, G., & Schiaffino, L. (2011) · The Journal of Organic Chemistry · doi:10.1021/jo102525t · Cited by 86 · see citing works
Gridnev, I. D., & Vorobiev, A. K. (2012) · ACS Catalysis · doi:10.1021/cs300497h · Cited by 84 · see citing works
Ribó, J. M., Blanco, C., Crusats, J., El‐Hachemi, Z., Hochberg, D., & Moyano, A. (2014) · Chemistry – A European Journal · doi:10.1002/chem.201404534 · Cited by 81 · see citing works
Spontaneous mirror symmetry breaking and origin of biological homochirality
Ribó, J. M., Hochberg, D., Crusats, J., El-Hachemi, Z., & Moyano, A. (2017) · Journal of The Royal Society Interface · doi:10.1098/rsif.2017.0699 · Cited by 68 · see citing works
Micheau, J.-C., Coudret, C., Cruz, J.-M., & Buhse, T. (2012) · Physical Chemistry Chemical Physics · doi:10.1039/c2cp42041d · Cited by 62 · see citing works
Dóka, É., & Lente, G. (2011) · Journal of the American Chemical Society · doi:10.1021/ja207408y · Cited by 60 · see citing works
Isotope Chirality and Asymmetric Autocatalysis: A Possible Entry to Biological Chirality
Barabás, B., Caglioti, L., Micskei, K., Zucchi, C., & Pályi, G. (2008) · Origins of Life and Evolution of Biospheres · doi:10.1007/s11084-008-9138-1 · Cited by 51 · see citing works
Data-Based Stochastic Approach to Absolute Asymmetric Synthesis by Autocatalysis
Barabás, B., Caglioti, L., Micskei, K., & Pályi, G. (2009) · Bulletin of the Chemical Society of Japan · doi:10.1246/bcsj.82.1372 · Cited by 36 · see citing works
Carter, D. J., Rohl, A. L., Shtukenberg, A., Bian, S., Hu, C., Baylon, L., Kahr, B., Mineki, H., Abe, K., Kawasaki, T., et al. (2012) · Crystal Growth & Design · doi:10.1021/cg300207d · Cited by 36 · see citing works
Kinetic Insight into Specific Features of the Autocatalytic Soai Reaction
Lavabre, D., Micheau, J.-C., Islas, J. R., & Buhse, T. (2007) · Topics in Current Chemistry · doi:10.1007/128_2007_149 · Cited by 34 · see citing works
- Authors
- Singleton, D. A., & Vo, L. K.
- Affiliations
- Texas A&M University (US)
- Corresponding author
- Singleton, Daniel A.
- ORCID
- Singleton, Daniel A.
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Published
- 2002-08-01
- Volume
- 124
- Issue
- 34
- Pages
- 10010-10011
- ISSN
- 0002-7863 (ISSN-L)
- 1520-5126
- OpenAlex
- W2063192409
- Cited by
- 118
- References
- 2
- Citations by year
- 2022: 8 · 2021: 4 · 2020: 4 · 2019: 2 · 2018: 1 · 2017: 4 · 2016: 1 · 2015: 4 · 2014: 8 · 2013: 4 · 2012: 8
- FWCI
- 7.82
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Journal of the American Chemical Society (publishedVersion)
- PubMed (publishedVersion)
- Funders
- National Institute of General Medical Sciences (R01GM045617, GM 45617)
- 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 › Chemistry and Stereochemistry Studies
- Keywords
- asymmetric autocatalysis, Soai reaction, asymmetric synthesis, absolute asymmetric synthesis, enantiomeric excess amplification, origin of homochirality, chiral amplification
- MeSH terms
- Methanol, Aldehydes, Chemistry, Organic, Pyrimidines, Stereoisomerism, Zinc
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