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

Anees Ahmad; Luiz F. Silva Jr.

doi:10.1055/s-0032-1317497

Synthesis, Inhaltsverzeichnis

Synthesis 2012; 44(23): 3671-3677
DOI: 10.1055/s-0032-1317497

paper

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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Abstract

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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

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Referenzen

References

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Some additional tests for 5a:

18a MeOH, BF₃·OEt₂, r.t., 2.5 h; 6a (27%) and 7a (23%).
18b TFE, BF₃·OEt₂, r.t., 30 min; 10a (23%).
18c MeCN, 0 °C; complex mixture.
18d HFIP–CH₂Cl₂ (1:4), 0 °C; complex mixture.
18e HFIP, 0 °C; unstable product.
18f HFIP, BF₃·OEt₂, 0 °C; no prominent spot on TLC.
18g CH₂Cl₂, 0 °C; complex mixture.
18h HFIP–CH₂Cl₂ (1:4), H₂O (22 equiv) 0 °C, NaBH₄; starting material recovered.

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Some additional tests for 5b:

20a MeOH, 0 °C, 40 min; 4-methoxy-4H-thiochromene (6b) (29%).
20b TMOF, 0 °C, 30 min; 4-methoxy-4H-thiochromene (6b) (38%).
20c TFE 0 °C; complex mixture.
20d HTIB, HFIP–CH₂Cl₂ (1:4), H₂O (22 equiv) 0 °C, NaBH₄; starting material recovered.

21 Ferraz HM. C, Carneiro VM. T, Silva LF. Jr. Synthesis 2009; 385

Some additional tests for 5f:

22a TFE, 0 °C; complex mixture.
22b MeCN, 0 °C; no prominent spot on TLC.
22c DMF, 0 °C; starting material recovered.
22d HFIP, 0 °C; no prominent spot on TLC.
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%).

Some additional tests for 5g:

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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