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Novel chemistry of alpha-tosyloxy ketones: applications to the solution- and solid-phase synthesis of privileged heterocycle and enediyne libraries

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningfagfællebedømt

  • K C Nicolaou
  • T Montagnon
  • Ulven, Trond
  • P S Baran
  • Y-L Zhong
  • F Sarabia
New synthetic technologies for the preparation and elaboration of alpha-tosyloxy ketones in solution- and on solid-phase are described. Both olefins and ketones serve as precursors to these relatively stable chemical entities: olefins via a novel one-pot epoxidation, arylsulfonic acid displacement, and oxidation sequence, and ketones by direct exposure to arylsulfonic acids in the presence of diacetoxy iodobenzene. Reaction of these substrates with O-, S-, or N-centered nucleophiles leads to incorporation of the nucleophile with concomitant expulsion of the sulfonate, while exposure to bis-functional nucleophiles furnishes annulated heterocyclic systems. In addition, the reactions of carbon-centered nucleophiles with alpha-tosylyloxy ketones are also explored. The collated data for all these nucleophiles provide compelling evidence for the proposal that different reaction pathways are followed when alpha-tosyloxy ketones are engaged by "hard" versus "soft" nucleophiles. The accessibility and site-selectivity of the chemistry demonstrated herein offer the promise of an expanded use for this moiety in solid-phase library construction, in particular, and in the field of organic synthesis, in general.
OriginalsprogEngelsk
TidsskriftAmerican Chemical Society. Journal
Vol/bind124
Udgave nummer20
Sider (fra-til)5718-5728
Antal sider11
ISSN0002-7863
StatusUdgivet - 22 maj 2002

ID: 189160785