Co2(CO)8-mediated endo mode cyclization of epoxy-alcohol: synthesis of 2-ethynyl-3-hydroxy-2-methyltetrahydropyran and 2-ethynyl-3-hydroxy-3-methyltetrahydropyran derivatives.

@article{Mukai2001Co2CO8mediatedEM,
  title={Co2(CO)8-mediated endo mode cyclization of epoxy-alcohol: synthesis of 2-ethynyl-3-hydroxy-2-methyltetrahydropyran and 2-ethynyl-3-hydroxy-3-methyltetrahydropyran derivatives.},
  author={Chisato Mukai and Sumie Yamaguchi and I. J. Kim and Miyoji Hanaoka},
  journal={Chemical \& pharmaceutical bulletin},
  year={2001},
  volume={49 5},
  pages={
          613-8
        }
}
Successive treatment of 4,5-epoxy-5-methyl-7-trimethylsilyl-6-heptyne-1-ol with Co2(CO)8 at 0 degrees C and a catalytic amount of BF3 x OEt2 at -78 degrees C gave the tetrahydropyran derivatives with the cobalt-complexed moiety. Similarly 4,5-epoxy-4-methyl-7-trimethylsilyl-6-heptyne-1-ol underwent ring closure under the above conditions to provide the corresponding tetrahydropyran derivatives. The preferential endo mode cyclization over the exo one was observed in these experiments. 
Synthetic and biosynthetic methods for selective cyclisations of 4,5-epoxy alcohols to tetrahydropyrans
TLDR
Synthetic approaches for endo-selective intramolecular epoxide ring opening (IERO) of 4,5-epoxy-alcohols and their applications in natural product synthesis are outlined and THP-containing natural products which utilise IERO reactions are reviewed.
A new entry to oxacycles via base-catalyzed endo mode cyclization of allenyl sulfoxides and sulfones.
TLDR
Treatment of the allenyl sulfoxides and sulfones possessing a proper delta-hydroxy appendage at the C-1 position with potassium tert-butoxide effected endo mode ring closure to provide the five- to eight-membered oxacycles in high yields.
An Approach to Cyclic α-Amino Acids by a Novel Hetero Diels-Alder/Intramolecular Hydantoin Enolate Alkylation Strategy: An Approach to Halichlorine
TLDR
Application of the present hetero Diels-Alder/intramolecular hydantoin alkylation methodology to synthesis of halichlorine was explored.
[Development of highly selective reactions based on metal carbonyls and its application to synthesis of bioactive compounds].
  • C. Mukai
  • Chemistry
    Yakugaku zasshi : Journal of the Pharmaceutical Society of Japan
  • 2002
TLDR
This review discusses the development of selective reactions based on alkyne-Co2 (CO)6 complexes, and their application to syntheses of bioactive compounds.
Synthesis of Marine Polycyclic Polyethers via Endo-Selective Epoxide-Opening Cascades
TLDR
This review summarizes how epoxide-opening cascade reactions have been used in the synthesis of ladder polyethers and oxasqualenoid natural products.
Epoxide-opening cascades in the synthesis of polycyclic polyether natural products.
TLDR
This review summarizes how epoxide-opening cascade reactions have been used in the synthesis of polycyclic polyethers and related natural products.
...
...

References

SHOWING 1-10 OF 12 REFERENCES
Stereocomplementary construction of 2-ethynyl-3-hydroxytetrahydrofuran derivatives via endo-mode ring closure of 3,4-epoxy-6-substitutedhex-5-yn-1-ols
Treatment of 3,4-epoxy-6-substitutedhex-5-yn-1-ols with BF3·OEt2 gave the endo-mode cyclization products with inversion of stereochemistry, whereas conversion of the epoxides to the corresponding
Stereoselective Total Synthesis of (+/-)-Swainsonine Based on Endo Mode Cyclization.
TLDR
A new stereoselective total synthesis of (+/-)-swainsonine is described, and the piperidine derivative thus prepared was converted into the title compound efficiently.
...
...