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.
11 Citations
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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.
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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.
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An Approach to Cyclic α-Amino Acids by a Novel Hetero Diels-Alder/Intramolecular Hydantoin Enolate Alkylation Strategy: An Approach to Halichlorine
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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].
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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
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This review summarizes how epoxide-opening cascade reactions have been used in the synthesis of ladder polyethers and oxasqualenoid natural products.
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This review summarizes how epoxide-opening cascade reactions have been used in the synthesis of polycyclic polyethers and related natural products.
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