The effect of leaving group orientation on solvolytic cope rearrangements. A study of exo-tricyclo[4.4.1.12,5]dodeca-3,7,9-trien-11-yl tosylates and derivatives.
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概要
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Synthesis and solvolytic behavior of derivatives of the highly hindered title compounds are described, <I>exo</I>-Tricyclo[4.4.1.1<SUP>2,5</SUP>]dodeca-3,7,9-trien-<I>syn</I>-yl tosylate (<I>syn</I>-<B>18</B>-OTs) and the corresponding perhydro derivative, <I>syn</I>-<B>23</B>-OTs, solvolyze at rates that are in reasonable agreement with those predicted by Foote-Schleyer calculations.<I>syn</I>-<B>18</B>-OTs, and its dihydro derivatives, <I>syn</I>-<B>19</B>-OTs and <I>syn</I>-<B>20</B>-OTs, give completely rearranged products on solvolysis in acetic acid and 75% dioxane, 80% acetone, and 75% dioxane, respectively (Table 2). These products can be explained by normal cationic rearrangements, probably occurring after ionization. On the other hand, <I>anti</I>-<B>18</B>-OTs and <I>anti</I>-<B>23</B>-OTs solvolyze at rates <I>ca.</I> 10<SUP>2</SUP> times slower than those predicted by Foote-Schleyer calculations. Presumably the <I>anti</I> derivatives of <B>18</B>-OTs, <B>20</B>-OTs, <B>23</B>-OTs, and the tetrahydro tosylate (<B>22</B>-OTs) suffer steric hindrance to ionization. Product formation from <I>anti</I>-<B>18</B>-OTs (Table 3) and <I>anti</I>-<B>19</B>-OTs in acetic acid and 75% dioxane, respectively, is explained as a [3<SUB>s</SUB>+3<SUB>s</SUB>] sigmatropic shift induced by ionization, with formation of an allylic ion providing the driving force for rearrangement.
- 公益社団法人 日本化学会の論文
著者
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FUJISE Yutaka
Department of Chemistry Hamamatsu University School of Medicine
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Ito Sho
Department Of Chemistry Faculty Of Science Tohoku University
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Itoh Isamu
Department of Chemistry, Tohoku University
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Nakatsu Tetsuo
Department of Chemistry, Tohoku University
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Senkler C.
Department of Chemistry, Princeton University
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Schleyer P.
Department of Chemistry, Princeton University
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