- Deamination Reactions, 52. - Cyclopropanediazonium Ions Derived form Propellanes
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Tricyclo1,6>dec-3-en-10-amines (16, 17) and their saturated analogs (18, 19) were prepared by a multistep sequence, starting from ethyl 2-oxo-cyclopentanecarboxylate (8).The intermediate tricyclo1,6>dec-3-ene-10-carboxylic acids (14) were separated and configurationally assigned by iodolactonization of the syn isomer.Nitrous acid deaminations of the amines 16 - 19 were preformed in aqueous lithium bromide solutions.Thus, the intervening carbocations were trapped to give stable tricyclic bromides 23 - 26 as the major products.Predominant retention of the configuration was observed with all substrates although the syn-amine 17 deviated significantly from its anti isomer 16 and from the higher homologs.Charge delocalization in the tricyclic cation 31 appears to be enhanced relative to the bicyclohex-3-yl cation (3). - Keywords: Diazonium Ions/ Nucleophilic displacement/ Propellanes/ Tricyclo1,6>dec-10-yl derivatives
- Kirmse, Wolfgang,Hellwig, Georg
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p. 393 - 396
(2007/10/02)
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