- 作者: 周德璋 ; 林耿弘 ; 葉雨林 等
- 作者服務機構: 中正大學化學系
- 中文摘要: A series of caged 1,4-diols, 26, 29a/29b, 31, were synthesized from the Diels-Alder cycloadduct 21 of 1,2,3,4- tetrachloro-5,5-dimethoxycyclopentadiene and 1,4- benzoquinone. Reduction of enedione 21 with aqueous TiCl/sub 3/, followed by base- catalyzed enolization in the presence of acetic anhydride, gave diene 23b, which reacted with maleic anhydride and 1,4-benzoquinone to produce the corresponding [ 4+2 ] cycloadducts 24b and 27, respectively. The adduct 24b was converted to birdcaged 1,4-diol 26 by photocyclization followed by decarboxylative olefination of resulted caged anhydride 25b. The adduct 27 was photocyclized to cage compound 28, which was aromatized to dihydroquinone 29a by acid-catalyzed enolization, or benzo- annulated compound 31 by reduction and dehydration. The birdcaged 1,4-diols 26 and 31 underwent fragmentation induced by (diacetoxyiodo)benzene to give enediones 38/39 and 41/42, respectively. Photocyclization of 38 and 39 produced the corresponding caged compounds 43 and 44, respectively, possessing homosecohexaprismane skeletons. The corresponding monohydrate 43a of 43 was structurally characterized by single-crystal X-ray diffraction.
- 英文摘要: --
- 中文關鍵字: Cage Compound; Diels Alder Reaction; Fragmentation; Photocyclization; Hexaprismane; Homosecohexaprismane
- 英文關鍵字: 籠化合物;Diels Alder反應;碎裂;光環化反應