Issue 21, 2003
From the journal:

Organic & Biomolecular Chemistry

Reflections on spontaneous asymmetric synthesis by amplifying autocatalysis†

Ilya D. Gridnev,*ab   Joerg M. Serafimov,a   Harry Quiney*c  and  John M. Brown*a  

* Corresponding authors

a Dyson Perrins Laboratory, South Parks Rd., Oxford, UK
E-mail: john.brown@chem.ox.ac.uk
Fax: 44 1865 275674
Tel: 44 1865 275742

b Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, JAPAN

c School of Chemistry, University of Melbourne, Victoria 3010, AUSTRALIA

Abstract

Spontaneous generation of chirality was observed in the course of studying the mechanism of asymmetric autocatalysis by NMR in ZnR2 alkylation of pyrimidin-5-aldehydes. A systematic study was carried out in order to discover its origins. Even in clean fresh non-glass reaction vessels spontaneous ee was clearly observed, and was not dependent on any single reaction parameter. For comparison it was demonstrated that enantiomerically pure Zn alkoxide catalyst could control the configuration of the reaction product even when present at below micromolar concentrations. The high propensity of the Soai reaction system to produce an enantiomerically enriched product without initial bias is suggested to result from stochastic effects. These are especially important in autocatalysis because all the final products can be derived by breeding from a small number of initial events. The statistical excess of one enantiomer in that set is sufficient to generate a measurable ee in the product. The process is aided by the requirement for dimerisation before the product is an active catalyst. An enumeration that rationalises these observations is provided.

Graphical abstract: Reflections on spontaneous asymmetric synthesis by amplifying autocatalysis

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Article information

DOI
https://doi.org/10.1039/B307382N
Article type
Paper
Submitted
27 Jun 2003
Accepted
15 Sep 2003
First published
06 Oct 2003

Org. Biomol. Chem., 2003,1, 3811-3819

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Reflections on spontaneous asymmetric synthesis by amplifying autocatalysis

I. D. Gridnev, J. M. Serafimov, H. Quiney and J. M. Brown, Org. Biomol. Chem., 2003, 1, 3811 DOI: 10.1039/B307382N

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