Asymmetric Autocatalysis and Its Implications for the Origin of Homochirality

Overview

Journal Proc Natl Acad Sci U S A

Specialty Science

Date 2004 Apr 7

PMID 15067112

Citations 52

Authors

Donna G Blackmond

Affiliations

Soon will be listed here.

Abstract

An autocatalytic reaction in which the reaction product serves as a catalyst to produce more of itself and to suppress production of its enantiomer serves as a mechanistic model for the evolution of homochirality. The Soai reaction provided experimental confirmation of this concept, nearly 50 years after it was first proposed. This Perspective offers a rationalization of the Soai autocatalytic reaction; accounting for enantiomeric excess and rate observations, that is both simple as well as gratifying in its implications for the chemical origin of life.

Citing Articles

Enhanced condensation kinetics in aqueous microdroplets driven by coupled surface reactions and gas-phase partitioning.

Li M, Yang S, Rathi M, Kumar S, Dutcher C, Grassian V Chem Sci. 2024; 15(33):13429-13441.

PMID: 39183898 PMC: 11339779. DOI: 10.1039/d4sc03014a.

Investigating chiral morphogenesis of gold using generative cellular automata.

Im S, Zhang D, Han J, Kim R, Choi C, Kim Y Nat Mater. 2024; 23(7):977-983.

PMID: 38693448 DOI: 10.1038/s41563-024-01889-x.

Symmetry breaking and chiral amplification in prebiotic ligation reactions.

Deng M, Yu J, Blackmond D Nature. 2024; 626(8001):1019-1024.

PMID: 38418914 DOI: 10.1038/s41586-024-07059-y.

Influence of the Weak Nuclear Force on Metal-Promoted Autocatalytic Strecker Synthesis of Amino Acids: Formation of a Chiral Pool of Precursors for Prebiotic Peptide and Protein Synthesis.

Cowan J Life (Basel). 2024; 14(1).

PMID: 38255681 PMC: 10817680. DOI: 10.3390/life14010066.

Profile of Donna G. Blackmond.

Viegas J Proc Natl Acad Sci U S A. 2024; 121(3):e2321815121.

PMID: 38190522 PMC: 10801848. DOI: 10.1073/pnas.2321815121.

References

Buono F, Blackmond D . Kinetic evidence for a tetrameric transition state in the asymmetric autocatalytic alkylation of pyrimidyl aldehydes. J Am Chem Soc. 2004; 125(30):8978-9. DOI: 10.1021/ja034705n. View

Gridnev I, Serafimov J, Quiney H, Brown J . Reflections on spontaneous asymmetric synthesis by amplifying autocatalysis. Org Biomol Chem. 2003; 1(21):3811-9. DOI: 10.1039/b307382n. View

Buono F, Iwamura H, Blackmond D . Physical and chemical rationalization for asymmetric amplification in autocatalytic reactions. Angew Chem Int Ed Engl. 2004; 43(16):2099-103. DOI: 10.1002/anie.200353086. View

Buschmann , Thede , HELLER . New Developments in the Origins of the Homochirality of Biologically Relevant Molecules The authors would like to thank the Fonds der Chemischen Industrie. Angew Chem Int Ed Engl. 2000; 39(22):4033-4036. DOI: 10.1002/1521-3773(20001117)39:22<4033::aid-anie4033>3.0.co;2-2. View

Kondepudi D, Asakura K . Chiral autocatalysis, spontaneous symmetry breaking, and stochastic behavior. Acc Chem Res. 2001; 34(12):946-54. DOI: 10.1021/ar010089t. View

Siegel J . Chemistry: shattered mirrors. Nature. 2002; 419(6905):346-7. DOI: 10.1038/419346a. View

Puchot C, Samuel O, Dunach E, Zhao S, Agami C, Kagan H . Nonlinear effects in asymmetric synthesis. Examples in asymmetric oxidations and aldolization reactions. J Am Chem Soc. 2011; 108(9):2353-7. DOI: 10.1021/ja00269a036. View

Girard C, Kagan H . Nonlinear Effects in Asymmetric Synthesis and Stereoselective Reactions: Ten Years of Investigation. Angew Chem Int Ed Engl. 2018; 37(21):2922-2959. DOI: 10.1002/(SICI)1521-3773(19981116)37:21<2922::AID-ANIE2922>3.0.CO;2-1. View

Feringa , van Delden RA . Absolute Asymmetric Synthesis: The Origin, Control, and Amplification of Chirality. Angew Chem Int Ed Engl. 1999; 38(23):3418-3438. DOI: 10.1002/(sici)1521-3773(19991203)38:23<3418::aid-anie3418>3.0.co;2-v. View

10.

Zielinski W, Orgel L . Autocatalytic synthesis of a tetranucleotide analogue. Nature. 1987; 327(6120):346-7. DOI: 10.1038/327346a0. View

11.

Saghatelian A, Yokobayashi Y, Soltani K, Ghadiri M . A chiroselective peptide replicator. Nature. 2001; 409(6822):797-801. DOI: 10.1038/35057238. View

12.

Paul N, Joyce G . A self-replicating ligase ribozyme. Proc Natl Acad Sci U S A. 2002; 99(20):12733-40. PMC: 130529. DOI: 10.1073/pnas.202471099. View

13.

Blackmond D, McMillan C, Ramdeehul S, Schorm A, Brown J . Origins of asymmetric amplification in autocatalytic alkylzinc additions. J Am Chem Soc. 2001; 123(41):10103-4. DOI: 10.1021/ja0165133. View

14.

Kondepudi D, Kaufman R, Singh N . Chiral symmetry breaking in sodium chlorate crystallizaton. Science. 1990; 250(4983):975-6. DOI: 10.1126/science.250.4983.975. View

15.

FRANK F . On spontaneous asymmetric synthesis. Biochim Biophys Acta. 1953; 11(4):459-63. DOI: 10.1016/0006-3002(53)90082-1. View

16.

Avalos M, Babiano R, Cintas P, Jimenez J, Palacios J, Barron L . Absolute Asymmetric Synthesis under Physical Fields: Facts and Fictions. Chem Rev. 2002; 98(7):2391-2404. DOI: 10.1021/cr970096o. View

17.

Welch C . Formation of highly enantioenriched microenvironments by stochastic sorting of conglomerate crystals: a plausible mechanism for generation of enantioenrichment on the prebiotic earth. Chirality. 2001; 13(8):425-7. DOI: 10.1002/chir.1055. View

18.

GILMAN J . Second supplementary list of parasitic fungi from Iowa. Iowa State Coll J Sci. 1949; 23(3):261-72. View

19.

Singleton D, Vo L . A few molecules can control the enantiomeric outcome. Evidence supporting absolute asymmetric synthesis using the Soai asymmetric autocatalysis. Org Lett. 2003; 5(23):4337-9. DOI: 10.1021/ol035605p. View