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Synthesis 1995; 1995(12): 1549-1561
DOI: 10.1055/s-1995-4141
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Synthesis of (-)-LL-C10037α and Related Manumycin-Type Epoxyquinols

Peter Wipf* , Yuntae Kim, Heike Jahn
  • *Department of Chemistry, University of Pittsburgh, Pennsylvania 15260, USA, Fax +1(412)6240787; E-mail pwipf+@pitt.edu
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Publication Date:
31 December 2000 (online)

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Starting with N-allyloxycarbonyl-protected 2,5-dimethoxyaniline, hypervalent iodine oxidation protocols and selective enone epoxidation provides the Streptomyces metabolite LL-C10037α in nine steps and 7-10% overall yield. In an asymmetric variant of this strategy, (R,R)-pentane-2,4-diol is used as a chiral acetalization agent. The resulting semiquinone spiroacetal, due to an ortho-acylamino substituent that restricts the 1,3-dioxane ring conformation, undergoes face-selective epoxidation and is further functionalized to give (-)-LL-C10037α in 94% ee. These pathways represent the first syntheses of the highly functionalized mC7N core of the manumycins and have been further extended toward the preparation of analogs for SAR studies of this class of antitumor antibiotics. Manumycins inhibit the farnesylation of Ras-protein by PFTase (protein farnesyltransferase).

hypervalent iodine oxidation - face-selective enone epoxidation - chiral quinone monoketals - antitumor antibiotics