Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Shape Selective Oxygen Transfer to Olefins Catalyzed by Sterically Hindered Iron Porphyrins

  • Ahn, Kwang-Hyun (Department of Chemistry, College of Natural Science, Kyung Hee University) ;
  • Groves, John T. (Department of Chemistry, Princeton University)
  • Published : 1994.11.20
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Abstract

Epoxidation of olefins catalyzed by iron-tetraarylporphyrins were studied to see the shape selectivity in the competing reaction between cis-and trans- or internal and external olefins. Cis-olefins were more reactive than trans-olefins in the competing reaction between cis-and trans-olefins. Interestingly, in the epoxidation of $cis-{\beta}-methystyrene$ by ${\alpha}{\beta}{\alpha}{\beta}$ atropisomer of Fe(III)TNPPPCl and iodosylbenzene, 27% of total product was phenylacetone. The unusually large amount of phenylacetone may be produced by hydride rearrangement of carbocationic intermediate. Regioselectivity of the reaction was also studied by using the most sterically hindered Fe(III)TTPPPCl. In the epoxidation of limonene with Fe(III)TTPPPCl, the disubstituted double bond was more reactive than trisubstituted double bond. This is in contrast to the results obtained with other iron-tetraarylporphyrins. Similar trend was also observed in the competing reaction between mono-and di-substituted olefins.

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