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Scientific article
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Über die thermische, katalytische und photochemische Stickstoff-Eliminierung des 1-Diazo-3-(1-methylcyclopenta-2,4-dienyl)-2-propanons

Other titleThe Thermal, Catalytic, and Photochemical Denitrogenation of 1-Diazo-3-(1-methylcyclopenta-2,4-dienyl)-2-propanone
Published inHelvetica chimica acta, vol. 69, no. 3, p. 676-682
Publication date1986-05-07
First online date2004-10-25
Abstract

The synthesis of the title compound 12 is described. This diazoketone, distinguished by its Cs-symmetry and by a built-in cisoid diene unit, gives 5-methyltricyclo[3.3.0.0²˙⁸]oct-6-ene-3-one (13) when subjected to thermal or catalytic denitrogenation with rhodium (II) acetate or copper (II) acetylacetonate. Direct irradiation of 12 at 350 nm causes Wolff rearrangement, whereas the benzophenone-sensitized photolysis gives again ketone 13. A 1,4-carbene or carbenoid addition was never observed under the conditions described. The ketone 13 equilibrates thermally or under base catalysis with 1-methyltricyclo[3.3.0.0²˙⁸]oct-6-ene-3-one (17). The key step of this apparent CH₃ migration is shown to be a Cope rearrangement of the corresponding enols (hydroxysemibullvalenes).

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Citation (ISO format)
BURGER, Ulrich, ZELLWEGER, Dominique. Über die thermische, katalytische und photochemische Stickstoff-Eliminierung des 1-Diazo-3-(1-methylcyclopenta-2,4-dienyl)-2-propanons. In: Helvetica chimica acta, 1986, vol. 69, n° 3, p. 676–682. doi: 10.1002/hlca.19860690318
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ISSN of the journal0018-019X
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