Catalytic ring-closing metathesis of doubly armed, bridged bicyclic sulfones. Evaluation of chain length and possible intramolecular SO2 group ligation to the ruthenium carbenoid

Leo A. Paquette, Fabrizio Fabris, Jinsung Tae, Judith C. Gallucci, John E. Hofferberth

Research output: Contribution to journalArticle

43 Citations (Scopus)

Abstract

Disubstituted bicyclic sulfones 3a-3d, which were prepared by the 2-fold alkylation of 1,6-dilithio-9-thiabicyclo[4.2.1]nonane dioxide, undergo ring- closing metathesis to give a select few of the possible dimers and trimers. Only in the case of 3d were monomeric end products formed. The pronounced diastereoselectivities observed, particularly with the two lowest homologues, are suggested to be kinetically favored because of the operation of internal ruthenium/sulfonyl oxygen coordination during generation of the first intermolecular double bond. This ligation appears to be an important component of the overall reaction in that it serves to maximize unfavorable nonbonded steric interactions when the sulfone bridges adopt a syn relationship. MM3 calculations indicate the anti sulfone dimers also to be thermodynamically favored when n = 3. The preference for the anti sulfone arrangement appears to erode with an increase in the length of the tethers. Not unexpectedly, a ring size dependency is likely at play. The development of a ring-closing metathesis strategy for the incorporation of sulfone groups into stereochemically defined polybicyclic molecules has been realized.

Original languageEnglish
Pages (from-to)3391-3398
Number of pages8
JournalJournal of the American Chemical Society
Volume122
Issue number14
DOIs
Publication statusPublished - 2000 Apr 12

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Sulfones
Ruthenium
Chain length
Dimers
Ligation
Alkylation
Molecules
Oxygen

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

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title = "Catalytic ring-closing metathesis of doubly armed, bridged bicyclic sulfones. Evaluation of chain length and possible intramolecular SO2 group ligation to the ruthenium carbenoid",
abstract = "Disubstituted bicyclic sulfones 3a-3d, which were prepared by the 2-fold alkylation of 1,6-dilithio-9-thiabicyclo[4.2.1]nonane dioxide, undergo ring- closing metathesis to give a select few of the possible dimers and trimers. Only in the case of 3d were monomeric end products formed. The pronounced diastereoselectivities observed, particularly with the two lowest homologues, are suggested to be kinetically favored because of the operation of internal ruthenium/sulfonyl oxygen coordination during generation of the first intermolecular double bond. This ligation appears to be an important component of the overall reaction in that it serves to maximize unfavorable nonbonded steric interactions when the sulfone bridges adopt a syn relationship. MM3 calculations indicate the anti sulfone dimers also to be thermodynamically favored when n = 3. The preference for the anti sulfone arrangement appears to erode with an increase in the length of the tethers. Not unexpectedly, a ring size dependency is likely at play. The development of a ring-closing metathesis strategy for the incorporation of sulfone groups into stereochemically defined polybicyclic molecules has been realized.",
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Catalytic ring-closing metathesis of doubly armed, bridged bicyclic sulfones. Evaluation of chain length and possible intramolecular SO2 group ligation to the ruthenium carbenoid. / Paquette, Leo A.; Fabris, Fabrizio; Tae, Jinsung; Gallucci, Judith C.; Hofferberth, John E.

In: Journal of the American Chemical Society, Vol. 122, No. 14, 12.04.2000, p. 3391-3398.

Research output: Contribution to journalArticle

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