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

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

• 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%).
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• 18d HFIP–CH₂Cl₂ (1:4), 0 °C; complex mixture.
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• 18g CH₂Cl₂, 0 °C; complex mixture.
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Some additional tests for 5b:
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• 20b TMOF, 0 °C, 30 min; 4-methoxy-4H-thiochromene (6b) (38%).
• 20c TFE 0 °C; complex mixture.
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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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