Functionalization of trans-decalin. III. A stereospecific preparation of vicinal cis two methyl groups of eremophilane skeleton, leading to dl-dehydrofukinone.

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概要

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• A procedure for the preparation of <I>dl</I>-dehydrofukinone (<B>1</B>), an eremophilane type sesquiterpene, from the diene adducts (<B>3</B>), prepared from the reaction of 4-methyl-3-methoxycarbonyl-2-cyclohexen-1-one with butadiene, is described. Acetalization-reduction (LiAlH<SUB>4</SUB>) of <B>3</B> followed by treatment of the corresponding mesylate with base provided 5,6-<I>cis</I>-5-methyltricyclo[4.4.1.0<SUP>1,6</SUP>]undec-8-en-2-one (<B>7</B>) in 69% overall yields. Reductive cleavage of <B>7</B> with lithium metal afforded <I>trans</I>-4β,4aβ-dimethyl-<I>Δ</I><SUP>6,7</SUP>-octalin-1-one (<B>8</B>), bearing a set of vicinal <I>cis</I> two methyl groups on the C-4 and C-4a carbons in an 83% yield. Functionalization of the double bond of <B>8</B> involves (1) reduction of carbonyl group and following tetrahydropyranylation, (2) epoxidation followed by regiospecific reduction of the oxirane ring at the C-6 position, and (3) subsequent oxidation of the hydroxyl group, giving <I>trans</I>-4aβ,5β-dimethyl-8β-tetrahydropyranyloxydecalin-2-one (<B>14b</B>) in good yields. The conversion of <B>14b</B> into the desired <B>1</B> was achieved smoothly by (1) hydrolysis of tetrahydropyranyl ether, (2) pyrolysis of its mesylate, and (3) subsequent aldol reaction with acetone followed with dehydration and isomerization of the double bond.

• 公益社団法人 日本化学会の論文

著者

• Inokuchi Tsutomu

  Department of Industrial Chemistry, School of Engineering, Okqyama University

関連論文

• Functionalization of trans-decalin. III. A stereospecific preparation of vicinal cis two methyl groups of eremophilane skeleton, leading to dl-dehydrofukinone.

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