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Mechanistic aspects of the lycopodine Michael-Claisen domino cyclization

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Abstract

The Michael-Claisen domino (MCD) cyclization used in the lycopodine synthesis by Stork, was evaluated mechanistically using DFT calculations. Calculations suggest that a dianion is not formed, which conforms to classical dianion formation normally requiring strong kinetic bases. Instead ethoxide in ethanol produces a monoanionic species driving the MCD cyclization. This endeavor has opened up potential to expand the scope of this unique reaction and provide educational clarity.

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Acknowledgments

The University of Queensland and the Friedrich-Schiller-Universität Jena for financial support, and computational time. CMW thanks the Australian Research Council for a Future Fellowship.

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Authors and Affiliations

  1. School of Chemistry and Molecular Biosciences, University of Queensland, Brisbane, 4072, Queensland, Australia

    Wilhelm A. Eger & Craig M. Williams

  2. Institut für Organische Chemie und Makromolekulare Chemie der Friedrich-Schiller-Universität Jena, Humboldtstrasse 10, 07743, Jena, Germany

    Wilhelm A. Eger & Ernst Anders

Authors
  1. Wilhelm A. Eger
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  2. Ernst Anders
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  3. Craig M. Williams
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Corresponding author

Correspondence to Craig M. Williams.

Additional information

This paper belongs to a Topical Collection on the occasion of Prof. Tim Clark’s 65th birthday

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Eger, W.A., Anders, E. & Williams, C.M. Mechanistic aspects of the lycopodine Michael-Claisen domino cyclization. J Mol Model 20, 2173 (2014). https://doi.org/10.1007/s00894-014-2173-0

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  • DOI: https://doi.org/10.1007/s00894-014-2173-0

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