トリシクロウンデカンのアダマンタン転位反応経路
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概要
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Pathways of the acid catalyzed multiple step isomerization (adamantane rearrangement) of tricycloundecanes are reviewed. 1. Introduction. Characteristics of adamantane rearrangements. 2. Rearrangement pathways of tricycloundecanes. 2.1 <I>cis</I>-<I>exo</I>- and -<I>endo</I>-Tetramethylenenorbornane (<I>exo</I>-7 and <I>endo</I>-7). (1) Structure determination of the intermediates. (2) Rearrangement of <I>cis</I>-<I>endo</I> tetramethylenenorbornane (<I>endo</I>-7) and that of the <I>exo</I>isomer (<I>exo</I>-7) in the presence of 1-methyl- adamantane. (3) Timeconversion studies. (4) Rearrangement pathways. 2.2 <I>cis</I>-2, 3-Trimethylenebicyclo [2.2.2] octane (20). (1) Structure determination of the intermediates. (2) Rearrangement pathways. 2.3 <I>cis</I>-<I>endo</I>-6, 7-Trimethylenebicyclo [3.2.1] octane (<I>endo</I>-14). 2.4 Enhancement of the rearrangement rate for endo vs. isomers in <I>cis</I>-2, 3-tetramethylenenorbornanes (7) and <I>cis</I>-6, 7-trimethylenebicyclo [3.2.1] octanes (14). 3. Rearrangement pathweys of tricycloundecanols and tricycloundecenes. 3.1 Hydride transfer reduction-rearrangement of <I>cis</I>-<I>exo</I>-5, 6-trimethylene-2-norbornyl carbinol (30), <I>cis</I>-<I>exo</I>-6, 7-trimethylenebicyclo [3.2.1] octan-2- and -endo-3-ol (31 and 32), and <I>cis</I>-<I>endo</I>-5, 6-trimethylenebicyclo [2. 2.2] octan-<I>exo</I>- and -<I>endo</I>-2-ol (33x and 33n). (1) Under sulfuric acid catalysis. (2) Under phosphoric acid catalysis. (3) Rearrangement pathways. 3.2 Hydride transfer reduction-rearrangement of <I>cis</I>-<I>exo</I>-2, 3-trimethylene-<I>endo</I>-2-hydroxymethylnorbornane (<I>exo</I>-34). 4. Preparative aspects of tricycloundecane rearrangement. 5. Conclusion. References.