The Regio- and Stereo-Selective Formation of Allylic Chlorides During the Overman Rearrangement of Trichloroacetimidates Derived from Certain Brominated Conduritols

Maria Matveenko; Anthony C. Willis; Martin G. Banwell

doi:10.1071/CH08438

RESEARCH ARTICLE

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The Regio- and Stereo-Selective Formation of Allylic Chlorides During the Overman Rearrangement of Trichloroacetimidates Derived from Certain Brominated Conduritols

Maria Matveenko ^A , Anthony C. Willis ^A and Martin G. Banwell ^A ^B

+ Author Affiliations

- Author Affiliations

^A Research School of Chemistry, Institute of Advanced Studies, The Australian National University, Canberra, ACT 0200, Australia.

^B Corresponding author. Email: mgb@rsc.anu.edu.au

Australian Journal of Chemistry 62(1) 64-68 https://doi.org/10.1071/CH08438
Submitted: 14 October 2008 Accepted: 20 November 2008 Published: 21 January 2009

Abstract

Microwave irradiation of imidate 2 at 165°C affords a ~3:1 mixture of the Overman rearrangement product 3 and the allylic chloride 4 (83% combined yield). Under the same conditions the deoxy-conduritol 6 gives a comparable mixture of compounds 7 and 8. The single-crystal X-ray structure of a derivative of chloride 8 is reported together with a mechanism that accounts for the selective formation of this compound and congener 4.

^* It is worth noting that the conversion 2 → 3 represents a rare example of a microwave-promoted Overman rearrangement^[⁵^] and seemingly only the second example of such a process involving a halogenated alkene.^[³^]

Acknowledgements

The authors thank the Institute of Advanced Studies and the Australian Research Council for financial support.

References

The Regio- and Stereo-Selective Formation of Allylic Chlorides During the Overman Rearrangement of Trichloroacetimidates Derived from Certain Brominated Conduritols

Abstract

Acknowledgements

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