Induced ionization in 1,4-diol monosuylfonate esters and its application in the synthesis of natural products

J.B.P.A. Wijnberg, Æ. de Groot

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The chemical manifestations of orbital interactions through four sigma-bonds in the base-induced and -directed reactions of monosulfonated tratis-perhydronaphthalene- and norbornane-1,4-diols are discussed. Through-bond interactions (TBI) and sigma-participation are the most important stereoelectronic effects which principally determine their reactivity. Dependent on the geometry of the relaying C-C bonds, these compounds react by three chief pathways: rearrangement, elimination, and homofragmentation. Substituents at carbon atoms adjacent to the carbon atom bearing the sulfonate ester group increase the contribution of sigma-participation, which-is expressed in a higher reactivity of these compounds. In cases where the ideal W arrangement is not distorted by alkyl substituents, the co-operation of TBI and sigma- participation results in a fast homofragmentation. Through-space interactions (TSI), if occurring next to TBI, have only a modest influence on the reactivity of these compounds. Secondary monosulfonate esters of rigid 1,4-diols do show these typical reactions after induced ionization but the ionization of primary sulfonate esters can not be induced in a similar way. The results obtained from the reactions on monomesylated cholestane-3,7-diols, as model systems for cyclic 1,5-diol monosulfonate esters, show that chemical consequences of TBI and sigma-participation still can be observed in these systems, but play only a minor role in their reaction patterns. Applications of reaction strategies in which orbital interactions through four sigma-bonds play an essential role are demonstrated in the total syntheses of cis-fused guaiane sesquiterpenes, alloaromadendrenes, alpha-santalanes and marasmanes.
Original languageEnglish
Pages (from-to)257-274
JournalCurrent Organic Chemistry
Issue number3
Publication statusPublished - 2003


  • perhydronaphthalene-1,4-diol monosulfonate esters
  • through-bond interaction
  • radical fragmentation/elimination sequence
  • 2-norbornyl para-toluenesulfonates
  • intramolecular electron-transfer
  • inductive charge dispersal
  • dictamnus-dasycarpus turcz
  • range or

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