71 C_2対称性を利用する酒石酸の新しい変換法とその光学活性天然物合成への応用

概要

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In order to synthesize optically active natural products which contain 1,2-glycol system or the related functionality in the molecule, a novel method for obtaining fully functionalized and protected tartaric acid derivatives was developed. Optically active tartaric acid esters (1 R'=Me, Et) were converted by utilizing a synthetic concept of C_2-symmetry of homotopic acetal ring (III) to optically active 6,8-dioxabicyclo[3.2.1]octanes (V) via β-arylsulfonylated acetals (IV X=SO_2Ar) in four or five steps sequence involving homologation step. Acetolysis of (V R^1=H) gave a new type of functionalized 3,4-dihydro-2H-pyrans (VI Y=R^1=H) in high yields. By effectively utilizing the method several optically and biologically active natural products, (+)-(1R,5S,7R)-exo-brevicomin (24)-an attractant pheromone of western pine beetle, (+)-(S,S)-(cis-6-methyl-tetrahydropyran-2-yl)acetic acid (28)-a constituent of civet, (-)-(S,S)-7,7-dimethyl-6,8-dioxabicyclo[3.2.1]octane (34)-an essential oil of Japanese hop, (-)-(S,S)-pestalotin (38)-a gibberellin synergist isolated from fungi, and (+)-(5S,6R)-6-acetoxy-5-hexadecanolide (44)-a mosquito oviposition attractant pheromone were synthesized enantiospecifically.
1983-09-15