Functionalization of trans-decalin. IV. A stereoselective synthesis of dl-.BETA.-costol, dl-arctiol, and the related eudesmane type sesquiterpenes.
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The efficient synthetic procedures to <I>dl</I>-β-costol (<B>1a</B>), <I>dl</I>-arctiol (<B>2</B>), and the related eudesmane type sesquiterpenes are described. <I>trans</I>-8,8-Ethylenedioxy-4aβ-methyldecalin-2α-ol (<B>6a</B>), prepared from <I>trans</I>-1,1-ethylenedioxy-4aβ-methyl-<I>Δ</I><SUP>6,7</SUP>-octalin by epoxidation and subsequent reduction of the epoxy ring, was converted into <B>1a</B> as follows: (1) deacetalization of <B>6a</B> followed with mesylation, giving 2α-methylsulfonyloxy-4aβ-methyldecalin-8-one (<B>7b</B>), (2) condensation of <B>7b</B> with methyl sodiomalonate and subsequent Wittig reaction with methylenetriphenylphosphorane affording dimethyl (<I>trans</I>-4aβ-methyl-1-methylene-7β-decalinyl)malonate (<B>9</B>), (3) reduction of sodium salt of <B>9</B> with NaAl(OCH<SUB>2</SUB>CH<SUB>2</SUB>OMe)<SUB>2</SUB>H<SUB>2</SUB>. Oxidation of <B>1a</B> with PCC gave <I>dl</I>-β-costsd. <I>dl</I>-Arctiol (<B>2</B>), structurally related to <B>1a</B>, was prepared from <I>trans</I>-5,5-ethylenedioxy-8aβ-methyldecalin-2-one. Introduction of two equatorial substituents, such as hydroxyl and 1-hydroxy-1-methylethyl groups at the C-2 and C-3 carbons of <B>2</B>, was carried out as follows: (1) methoxycarbonylation followed by methylation of the sodium salt of keto ester with MeLi, (2) subsequent reduction with lithium in liquid NH<SUB>3</SUB>, giving <I>trans</I>-5,5-ethylenedioxy-3β-(1-hydroxy-1-methylethyl)-8aβ-methyldecalin-2α-ol (<B>14</B>), and (3) deacetalization of <B>14</B> followed by the reaction with methylenetriphenylphosphorane. <I>dl</I>-Eudesma-4(14),7(11)-dien-8-one was also prepared from <B>2</B> by oxidation with PCC followed by dehydration and subsequent isomerization of double bond.
- 公益社団法人 日本化学会の論文
著者
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Torii Sigeru
Department Of Applied Chemistry Faculty Of Engineering Okayama University
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Inokuchi Tsutomu
Department Of Applied Chemistry Faculty Of Engineering Okayama University
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