Cyclization of an alkene-bearing cyclopentanone: The role of rhodium and Brønsted acid

Xin Jiang, Zhongda Pan, Christopher J. Douglas

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5 Scopus citations

Abstract

The cyclization of an alkene-bearing cyclopentanone to a [2.2.1]-norcamphor ring system is described. The reaction is catalyzed by a combination of rhodium and Brønsted acid. Control experiments indicate that both are needed for acceptable yield. Control experiments with bulky base additives show that rhodium promotes alkene isomerization, likely the first step of this cascade reaction, and that rhodium alone does not promote cyclization. Cyclization is promoted by Brønsted acid in a Prins-type cyclization and carbocation rearrangement process. Trace Brønsted acid present in commercial samples of Rh(cod)2OTf is likely responsible for the observed reaction. Indeed, the norcamphor product can be obtained simply with strong acid, presumably initiated by acid-promoted alkene isomerization. Since our initial motivation for this work was the development of rhodium catalysts for the activation of C-C bonds adjacent to ketones, this communication serves to identify other, perhaps less obvious, pathways for the reactions of unsaturated ketone compounds by the action of rhodium catalysts.

Original languageEnglish (US)
Pages (from-to)5324-5327
Number of pages4
JournalTetrahedron Letters
Volume56
Issue number39
DOIs
StatePublished - Aug 22 2015

Bibliographical note

Funding Information:
We thank the National Science Foundation ( CHE-1151547 ) for funding. NMR spectra were recorded on an instrument purchased with support from the National Institute of Health ( S10 OD011952 ).

Keywords

  • Acid-mediated
  • Cyclopentanone
  • Rearrangement
  • Rhodium

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