Reflections on spontaneous asymmetric synthesis by amplifying autocatalysis

Ilya D. Gridnev, Joerg M. Serafimov, Harry Quiney, John M. Brown

Research output: Contribution to journalArticle

100 Citations (Scopus)

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 enantiometrically enriched product without initial basis 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.

Original languageEnglish
Pages (from-to)3811-3819
Number of pages9
JournalOrganic and Biomolecular Chemistry
Volume1
Issue number21
DOIs
Publication statusPublished - 2003 Nov 7

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry

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