RuO4-promoted oxidative polycyclization of isoprenoid polyenes. A further insight into the stereochemistry of the process

Abstract Further studies on the RuO4-catalyzed oxidative polycyclization of isoprenoid polyenes have been carried out. The configuration of the tris-THF product from the oxidation of geranylgeranyl acetate has been determined by a combination of spectral and chemical correlation methods. The oxidation of (E,Z)-farnesyl acetate, synthesized from nerol, has been carried out. This process stops at the first cyclization indicating that an E configuration of the Δ6 double bond is needed for the second cyclization to occur. The results are discussed in comparison with previous knowledge on the related Re(VII) polycyclization of polyenic bis-homoallylic alcohols.

[1]  R. Gibbs,et al.  Synthesis and biological evaluation of the geometric farnesylated analogues of the a-factor mating peptide of Saccharomyces cerevisiae. , 2000, The Journal of organic chemistry.

[2]  Kazuhiro Tanaka,et al.  Stereoselective total synthesis of lysocellin, the representative polyether antibiotic of the lysocellin family. Part 2. Synthesis of C10–C23 subunit via construction of two rings (B and C) and its condensation with C1–C9 subunit to achieve the total synthesis of lysocellin , 1996 .

[3]  F. McDonald,et al.  Sequential application of stereoselective syn-oxidation methodologies to natural product synthesis: A potentially biomimetic approach to the C12–C21 bistetrahydrofuran region of monensin , 1997 .

[4]  Y. Morimoto,et al.  Effective Combination of Two-Directional Synthesis and Rhenium(VII) Chemistry: Total Synthesis of meso Polyether Teurilene , 1999 .

[5]  J. McLaughlin,et al.  Annonaceous acetogenins: recent progress. , 1999, Journal of natural products.

[6]  T. Donohoe,et al.  Hydrogen bonding control in the oxidative cyclisation of 1,5-dienes , 2001 .

[7]  E. Keinan,et al.  Rules of Stereoselectivity in Tandem Oxidative Polycyclization Reaction with Rhenium(VII) Oxides , 1998 .

[8]  F. McDonald,et al.  Acylperrhenate-Induced Tandem syn-Oxidative Cyclizations of Hydroxydienes , 1995 .

[9]  R. Hughes,et al.  Diastereoselective synthesis of tetrahydrofuran-containing fragments by the permanganate oxidation of 1,5,9-trienes , 2000 .

[10]  F. Sum,et al.  Stereoselective synthesis of β-substituted α,β-unsaturated esters by dialkylcuprate coupling to the enol phosphate of β-keto esters , 1979 .

[11]  E. Keinan,et al.  Oxidative polycyclizations with rhenium(VII) oxides , 2002 .

[12]  Y. Morimoto,et al.  Highly Diastereoselective Cyclizations of Bishomoallylic Tertiary Alcohols Promoted by Rhenium(VII) Oxide. Critical Steric versus Chelation Effects in Alkoxyrhenium Intermediates , 1998 .

[13]  N. Oberlies,et al.  Recent advances in Annonaceous acetogenins. , 1996, Natural product reports.