12,13-Epoxy-C-nor-D-homosteroids. IV. The reaction of 11-oxygenated 17.ALPHA.-acetyl-12.ALPHA.,13.ALPHA.-epoxyetiojervanes with boron trifluoride etherate.
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概要
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The titled compounds were treated with boron trifluoride etherate in benzene at room temperature, 11α-Hydroxy-12α,13α-epoxide (<B>1</B>) underwent rapid cleavage of the epoxy ring at both C<SUB>13</SUB> and C<SUB>12</SUB> to give 11α-hydroxy-13β-fluoro-12α-alcohol (<B>2</B>), 13α-hydroxy-12β-11-ketone (<B>3</B>), 17-deacetyl-<I>Δ</I><SUP>12</SUP>-11-ketone (<B>4</B>), and an acetophenone derivative (<B>5</B>) in comparative yields. The same acid treatment of 11α-acetoxy-12α,13α-epoxide (<B>1a</B>) yielded 11α-acetoxy-13β-fluoro-12α-alcohol (<B>2a</B>) as a single isolable product, while that of 11-unsubstituted 12α,13α-epoxide (<B>16</B>) afforded 12β-fluoro-13α-alcohol (<B>17</B>) besides <B>5</B>, a major product. Evidently, compounds <B>2a</B> and <B>17</B> are products formed by the epoxy ring opening at C<SUB>13</SUB> and C<SUB>12</SUB> respectively. Interestingly, compounds <B>2</B> and <B>2a</B>, when treated with bases, produced a rearranged 13α-pregnane derivative (<B>12</B>) <I>via</I> 11α, 12α-dihydroxy-<I>Δ</I><SUP>13(17)</SUP>-20-ketone (<B>10</B>), in good yields. On the other hand, the epoxy cleavage of 11-oxo-12α,13α-epoxide (<B>13</B>) led to predominant formation of rearranged products, bicyclo[3.3.1]nonane-2,9-dione and hydrooxepin derivatives (<B>14</B> and <B>15</B>). It is emphasized that the epoxy cleavage reactions proceeded more slowly and took place at C<SUB>13</SUB> rather than at C<SUB>12</SUB> with increase of electronegativity of the 11-substituents.
- 公益社団法人 日本化学会の論文
著者
-
Murai Akio
Department Of Chemistry Faculty Of Science Hokkaido University
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Masamune Tadashi
Department Of Chemistry Faculty Of Science Hokkaido University
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Sasamori Hiroshi
Department of Chemistry, Faculty of Science, Hokkaido University
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