Oxidative polycyclizations with rhenium(VII) oxides*
Ehud Keinan1,2 and Subhash C. Sinha2
1Department of Chemistry and Institute of Catalysis
Science and Technology, Technion-Israel Institute of Technology, Technion
City, Haifa 32000, Israel; 2Department of Molecular Biology and The
Skaggs Institute for Chemical Biology, The Scripps Research Institute,
10550 North Torrey Pines Road, La Jolla, CA 92037, USA
Abstract: The consecutive oxidative polycyclization reaction
with rhenium(VII) oxides represents a highly stereoselective synthetic
tool by which polyenes that contain a bis-homoallylic alcohol can be
transformed into poly-THF products in a single step. On the basis of
a detailed study with model substrates, a set of rules is proposed to
predict product configurations in the polycyclization reactions with
trifluoroacetylperrhenate. This methodology is exceptionally useful
for the synthesis of polyoxygenated carbon skeletons that contain many
stereogenic centers, and for the Annonaceous acetogenins in particular.
Many of these potent antitumor agents, including solamin, reticulatacin,
asimicin, bullatacin, trilobin, trilobacin, squamotacin, rolliniastatin,
uvaricin, rollidecins C and D, mucocin, goniocin, and cyclogoniodenin
T, as well as chemical libraries of non-natural analogs, were synthesized
using the oxidative polycyclization reaction in combination with the
Sharpless AD and AE reactions.
*Lecture presented at the 11th IUPAC International
Symposium on Organometallic Chemistry Directed Towards Organic Synthesis
(OMCOS-11), Taipei, Taiwan, 22-26 July 2001. Other presentations are
presented in this issue, pp.1-186.
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