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Synthesis 2012; 44(23): 3671-3677
DOI: 10.1055/s-0032-1317497
paper
© Georg Thieme Verlag Stuttgart · New York

Synthesis of Chromanes and 4H-Chromenes: Exploring the Oxidation of 2H-Chromenes and Dihydro-1-benzoxepines by Hypervalent Iodine(III)

Anees Ahmad
Instituto de Química - Universidade de São Paulo, Av. Prof. Lineu Prestes, 748, CP 26077, CEP 05513-970 São Paulo SP, Brazil   Fax: +55(113)8155579   Email: luizfsjr@iq.usp.br
,
Luiz F. Silva Jr.*
Instituto de Química - Universidade de São Paulo, Av. Prof. Lineu Prestes, 748, CP 26077, CEP 05513-970 São Paulo SP, Brazil   Fax: +55(113)8155579   Email: luizfsjr@iq.usp.br
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Publication History

Received: 09 August 2012

Accepted: 02 October 2012

Publication Date:
17 October 2012 (online)

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Abstract

The reaction of various oxygen-containing benzo-fused cycloalkenes were studied with the hypervalent iodine reagent hydroxy(tosyloxy)iodo]benzene­ [PhI(OH)OTs, HTIB]. 2H-Chromene and 4-methyl-2H-chromene resulted in substituted 4H-chromene and cis-3,4-dialkoxy-4-methyl-3,4-dihydro-2H-chromenes, respectively. Ring contraction to chromanes and benzofurans was observed for dihydrobenzoxepines and 2,2-dimethyl-2H-chromenes, respectively.

Key words

chromenes - chromanes - Koser’s reagent - ring contraction - hypervalent iodine

Supporting Information

    for this article is available online at http://www.thieme-connect.com/ejournals/toc/synthesis.
  • Supporting Information
 

  • References

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    • 18a MeOH, BF3·OEt2, r.t., 2.5 h; 6a (27%) and 7a (23%).
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    • 22c DMF, 0 °C; starting material recovered.
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    • 22e PhI(OAc)2 (1.1 equiv), MeOH, 0 °C; starting material recovered.
    • 22f PhI(OAc)2 (1.1 equiv), MeOH, BF3·OEt2, 0 °C; 18f (12%).
    • 22g TMOF, 0 °C; 18f (13%).

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    • 23a TFE, 0 °C; complex mixture.
    • 23b MeCN, 0 °C; complex mixture.
    • 23c HFIP–CH2Cl2 (1:4), 0 °C; complex mixture.
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