Triflimide-catalysed sigmatropic rearrangement of n-allylhydrazones as an example of a traceless bond construction

ABSTRACT The recognition of structural elements (that is, retrons) that signal the application of specific chemical transformations is a key cognitive event in the design of synthetic routes

to complex molecules. Reactions that produce compounds without an easily identifiable retron, by way of either substantial structural rearrangement or loss of the atoms required for the

reaction to proceed, are significantly more difficult to apply during retrosynthetic planning, yet allow for non-traditional pathways that may facilitate efficient acquisition of the target

molecule. We have developed a triflimide (Tf2NH)-catalysed rearrangement of _N_-allylhydrazones that allows for the generation of a sigma bond between two unfunctionalized _sp_3 carbons in

such a way that no clear retron for the reaction remains. This new ‘traceless’ bond construction displays a broad substrate profile and should open avenues for synthesizing complex molecules

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Article  CAS  Google Scholar  Download references ACKNOWLEDGEMENTS This work was supported by the National Science Foundation (CHE0845063), the donors of the American Chemical Society

Petroleum Research Fund (grant no. 46778-G) and Northwestern University. AUTHOR INFORMATION AUTHORS AND AFFILIATIONS * Department of Chemistry, Northwestern University, Evanston, 60208,

Illinois, USA Devon A. Mundal, Christopher T. Avetta Jr & Regan J. Thomson Authors * Devon A. Mundal View author publications You can also search for this author inPubMed Google Scholar

* Christopher T. Avetta Jr View author publications You can also search for this author inPubMed Google Scholar * Regan J. Thomson View author publications You can also search for this

author inPubMed Google Scholar CONTRIBUTIONS R.J.T. conceived the idea and wrote the manuscript. D.A.M. and C.T.A. performed the experiments. All the authors analysed the data, contributed

to discussions and edited the manuscript. CORRESPONDING AUTHOR Correspondence to Regan J. Thomson. ETHICS DECLARATIONS COMPETING INTERESTS The authors declare no competing financial

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Mundal, D., Avetta, C. & Thomson, R. Triflimide-catalysed sigmatropic rearrangement of _N_-allylhydrazones as an example of a traceless bond construction. _Nature Chem_ 2, 294–297

(2010). https://doi.org/10.1038/nchem.576 Download citation * Received: 17 September 2009 * Accepted: 19 January 2010 * Published: 28 February 2010 * Issue Date: April 2010 * DOI:

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