Addition of carbon nucleophiles to arene-chromium complexes

M. F. Semmelhack, G. R. Clark, J. L. Garcia, J. J. Harrison, Y. Thebtaranonth, W. Wulff, A. Yamashita

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Abstract

The electrophilic reactivity of arenes coordinated to the chromium tricarbonyl unit has been developed into several distinct methods for coupling carbon nucleophiles with aromatic rings. Addition of the nucleophile produces stable η5-cyclohexadienyl chromium complexes which can be oxidized to induce loss of the endo hydrogen and the metal, overall nucleophilic substitution for hydrogen. Alternatively, the intermediate can be protonated and the resulting cyclohexa-1,3-diene can be detached from the chromium, effecting nucleophilic addition with reduction of one double bond. If a halogen (F, Cl) is present as a ring substituent, and if the nucleophile can migrate about the arene ligand, then loss of halide can occur parallel with classical nucleophilic aromatic substitution for halogen in electron-deficient haloarenes. With substituted arenes, the regioselectivity of addition becomes important and is often very high. Particularly useful are strong resonance donor substituents (RO-, R2N-, F-) where selectivity for meta attack is high. Indole provides an excellent example of selective activation, as the six-membered ring complexes selectively and is then susceptible to nucleophilic substitution, predominantly at the 4 and 7 positions. Substitution for halogen is a somewhat limited process and depends upon the nature of the nucleophile. Very reactive nucleophiles add to unsubstituted positions and are often slow to isomerize to the ipso position from which loss of halide can occur.

Original languageEnglish (US)
Pages (from-to)3957-3965
Number of pages9
JournalTetrahedron
Volume37
Issue number23
DOIs
StatePublished - 1981

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

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