Revisiting Staudinger and Ruzicka’s altered pyrethrolone: the cyclopentadienone dimers derived from pyrethrin I, cinerin I and jasmolin I

Oliver E. Hutt; Jamie A. Freemont; Stella Kyi; Stuart W. Littler; Ross P. McGeary; Peter J. Duggan; John Tsanaktsidis; Helen F. Cole; Maurice G. Kerr; Elizabeth H. Krenske; John H. Ryan

doi:10.1071/CH23197

RESEARCH ARTICLE (Open Access)

Previous Contents Vol 77(3)

Revisiting Staudinger and Ruzicka’s altered pyrethrolone: the cyclopentadienone dimers derived from pyrethrin I, cinerin I and jasmolin I

Oliver E. Hutt ^A , Jamie A. Freemont ^A , Stella Kyi ^A , Stuart W. Littler ^A , Ross P. McGeary ^B , Peter J. Duggan

^A ^C , John Tsanaktsidis ^A , Helen F. Cole ^D , Maurice G. Kerr ^D , Elizabeth H. Krenske

^B and John H. Ryan

^A ^*

+ Author Affiliations

- Author Affiliations

^A CSIRO Manufacturing, Ian Wark Laboratory, Bayview Avenue, Clayton, Vic. 3168, Australia.

^B School of Chemistry and Molecular Biosciences, The University of Queensland, St Lucia, Qld 4072, Australia.

^C College of Science and Engineering, Flinders University, Adelaide, SA 5042, Australia.

^D Botanical Resources Australia Pty Ltd, 44-46 Industrial Drive, Ulverstone, Tas. 7315, Australia.

^* Correspondence to: jack.ryan@csiro.au

Handling Editor: Craig Hutton

Australian Journal of Chemistry 77, CH23197 https://doi.org/10.1071/CH23197

Submitted: 24 October 2023 Accepted: 14 February 2024 Published online: 8 March 2024

© 2024 The Author(s) (or their employer(s)). Published by CSIRO Publishing. This is an open access article distributed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License (CC BY-NC-ND)

Abstract

The reactions of pyrethrin I, cinerin I and jasmolin I with sodium hydroxide in ethanol afforded an approximately 1:1 ratio of two respective cyclopentadienone dimers, isolated in good yield. A combination of one-dimensional and two-dimensional NMR spectroscopic studies allowed determination of the structure and stereochemistry of the dimers. The dimers are formed by cycloaddition reactions of the less substituted alkene of the cyclopentadienone, and by regioisomeric endo transition states. Density functional theory calculations were in accord with the experimental findings showing the products formed by ambimodal transition states. One such transition state led to two initial products with the less stable product undergoing facile conversion to the other more stable, experimentally observed product. These studies clarify the structures of the altered pyrethrolone reported by Staudinger and Ruzicka in 1924.

Keywords: altered pyrethrolone, biologically active molecules, cinerin I, cyclopentadienone, density functional calculations, dimerisation, electrocyclic reactions, elimination, jasmolin I, pyrethrin I.

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