On the Ability of Formaldehyde to Act as a Tethering Catalyst in Water
- 590 Downloads
The low concentration issue is a fundamental challenge when it comes to prebiotic chemistry, as macromolecular systems need to be assembled via intermolecular reactions, and this is inherently difficult in dilute solutions. This is especially true when the reactions are challenging, and reactions that proceeded more rapidly could have dictated chemical evolution. Herein we establish that formaldehyde is capable of catalyzing, via temporary intramolecularity, a challenging reaction in water at low concentrations, thus providing an alternative to other approaches that can either lead to higher concentrations or higher effective molarities.
KeywordsCatalysis Molecular evolution Formaldehyde Temporary intramolecularity Low concentration issue Prebiotic chemistry
We thank the University of Ottawa and the Natural Sciences and Engineering Research Council (NSERC) of Canada for generous financial support. M.P.J. thanks the Ontario Graduate Scholarship and M.P.J. and M.J.M. thanks NSERC for graduate scholarships. We also thank Dr. Claudia El Nachef for stimulating discussions.
Compliance with Ethical Standards
The authors declare no competing financial interest.
- Cairns-Smith AG, Hartman H (1987) Clay minerals and the origin of life. Cambridge University Press, UKGoogle Scholar
- Carey MF, Peterson CL, Smale ST (2009) Chromatin immunoprecipitation (ChIP). Cold Spring Harb Protoc 4:1–8Google Scholar
- Diederich F, Stang PJ (2000) Templated organic synthesis. Wiley-VCH, ChichesterGoogle Scholar
- Fratzke ARJ (1985) Kinetic analysis of the dimerization and disproportionation of aqueous glyoxal. Iowa State University, DissertationGoogle Scholar
- Guimond N, MacDonald MJ, Lemieux V, Beauchemin AM (2012) Catalysis through temporary intramolecularity: mechanistic investigations on aldehyde-catalyzed cope-type hydroamination lead to the discovery of a more efficient tethering catalyst. J Am Chem Soc 134:16571–16577Google Scholar
- Hesp CR, MacDonald MJ, Zahedi MM, Bilodeau DA, Zhao S, Pesant M, Beauchemin AM (2015) Formaldehyde as tethering organocatalyst: highly diastereoselective hydroaminations of allylic amines. Org Lett 17:5136–5139Google Scholar
- Shah DO (1972) The origin of membranes and related surface phenomena. In: Ponnamperuma C (ed) Exobiology, vol 23. North-Holland, Amsterdam, pp 235–265Google Scholar
- Taillades J, Beuzelin I, Garrel L, Tabacik V, Bied C, Commeyras A (1998) N-Carbamoyl-α-amino acids rather than free α-amino acids formation in the primitive hydrosphere: a novel proposal for the emergence of prebiotic peptides. Origins Life Evol Biosphere 28:61–77Google Scholar