Synthesis of methyl-1,6-dioxaspiro[4,5]decanes using organoselenium mediated cyclization reactions

doi:10.1016/S0040-4039(00)85671-3

Tetrahedron Letters

Volume 23, Issue 44, 1982, Pages 4625-4628

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Abstract

Three naturally occurring methyl-1,6-dioxaspiro[4.5]decanes have been prepared in good yield using organoselenium mediated reactions during the crucial cyclization process.

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A diastereoselective approach to (2R,5S)- and (2S,5S)-2-methyl-1,6-dioxaspiro[4.5]decane 1 and 1a is described. The route starts with an alkylation reaction among the cyclopentanone N,N-dimethylhydrazone 6 and the chiral iodides (R)-3 or (S)-3, derived from the enantiomers of ethyl β-hydroxybutyrate, controlling the estereocenter at C-2 of the molecules. The alkylated products 7 and 7a were easily transformed into the 1,8-O-TBS-1,8-dihydroxy-5-nonanones 9 and 9a in four steps, and a subsequent stereoselective spiroketalization, in acidic media, afforded a Z:E mixture (1:2) of compounds 1 and 1a.

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Synthesis of methyl-1,6-dioxaspiro[4,5]decanes using organoselenium mediated cyclization reactions

Abstract

J. Chem. Soc., Chem. Commun.

J. Chem. Soc., Chem. Commun.

Tetrahedron

Angew. Chem. Int., Ed. Engl.

Chem. Ber.

Tetrahedron Lett.

Synthetic Chemistry of Insect Pheromones and Juvenile Hormones