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Issue 21, 2003
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Reflections on spontaneous asymmetric synthesis by amplifying autocatalysis

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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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Publication details

The article was received on 27 Jun 2003, accepted on 15 Sep 2003 and first published on 06 Oct 2003


Article type: Paper
DOI: 10.1039/B307382N
Citation: 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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