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Stereoinduction by distortional asymmetry

Nature Chemistry volume 2, pages 303–307 (2010)Cite this article

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Abstract

Stereoselective chemical synthesis requires the two faces of a π bond to be differentiated. Theoretically sound qualitative models for understanding stereoinduction seem to break down in sterically unbiased cyclic systems. Presented here as the distortional asymmetry model is new insight that identifies circumstances where distortional ground state contributions are highly asymmetric and thereby contribute significantly to face selectivity. Out-of-plane distortional potential calculations, transition state calculations and molecular orbital analysis agree with experimental data that cannot otherwise be attributed to steric, torsion, polar or emergent transition state stabilizing effects. The model is readily understood in terms of reaction theory. The explanatory power of the model is also discussed.

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Figure 1: Epoxidation of sterically unbiased olefins.
Figure 2: Distortional asymmetry profile.
Figure 3: Origin and consequences of asymmetric distortional contributions to face selectivity.
Figure 4: Asymmetric bonding interactions. Ring strain perturbs the π bond and gives rise to increased orbital interactions.

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Acknowledgements

Support from Merck is gratefully acknowledged.

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Authors and Affiliations

  1. Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, New Brunswick, 08903, New Jersey, USA.

    Robert V. Kolakowski & Lawrence J. Williams

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  1. Robert V. Kolakowski
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  2. Lawrence J. Williams
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Contributions

L.J.W. and R.V.K. designed experiments and analysed data, R.V.K. performed experiments, and L.J.W. wrote the paper.

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Correspondence to Lawrence J. Williams.

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The authors declare no competing financial interests.

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Kolakowski, R., Williams, L. Stereoinduction by distortional asymmetry. Nature Chem 2, 303–307 (2010). https://doi.org/10.1038/nchem.577

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