臺灣博碩士論文加值系統

中文摘要
在本論文中，我們首先製備了幾個具有trans-2-allyl-, vinyl- and phenylcycloalkyl 取代基的α-偶氮-β-酮腈類化合物；並對其分子內環丙化反應進行了研究。以Rh2(OAc)4 (1 mol%) 為催化劑於CH2Cl2溶液中，我們發現allyl- 和vinyl- 取代的偶氮底物可順利地進行環丙化反應，以47-88%的產率生成具有並聯三環骨架的α-酮基環丙腈。加成均是以立體選擇性的方式進行，產物的dr值為79:21到＞99:1。當相同的催化條件時應用於phenylcycloalkyl 取代的底物時，反應並未給出任何環丙烷產物結構，而是產生六氫菲類或四氫環戊萘衍生物。我們推測此產物可能是由norcaradiene 中間體開環而得。
此外我們還發現所得到的α-酮基環丙腈在電子給予體的作用下可發生開環或1,3-cyano遷移反應，從而證實電子所促成的還原過程應首先發生在酮基而非氰基。

Abstract
Several α-diazo-β-ketonitriles bearing trans-2-allyl-, vinyl- and phenylcycloalkyl groups were synthesized and investigated for intramolecular cyclopropanation. Under the catalysis of Rh2(OAc)4 (1 mol%) in CH2Cl2, the cyclopropanation reactions of the allyl- and vinyl-substituted precursors could occur smoothly at ambient temperature, affording the novel tricyclic α-ketocyclopropylnitriles in synthetically useful yields (47-88%) with drs ranging from 79:21 to ＞ 99:1. On the other hand, the catalytic reactions of the phenyl-containing analogues did not give any cyclopropyl products, but rather provided the functionalized hexahydrophenanthrenes or tetrahydrocyclopentanaphthalene presumably resulted from the ring-opening of norcaradiene intermediates.
In addition, the resulting α-ketocyclopropylnitriles were demonstrated to undergo a cyclopropane ring-opening and/or a 1,3-cyano migration upon treatment with electron-donating reagent, thus validating the electron-mediated reaction should occur primarily on the keto moiety rather than on the nitrile group.

目錄
中文摘要 i
英文摘要 ii
謝誌 iii
目錄 v
縮寫符號對照表 vi

銠催化α-偶氮-β-酮腈類化合物分子內環丙化反應之研究 1
第一節 緒論 1
第二節 結果與討論 7
2.1 2-Allyl- 和 2-vinylcycloalkyl取代α-diazo-β-ketonitrile底物分子內環丙烷化反應 7
2.2 2-Phenylcycloalkyl取代α-diazo-β-ketonitrile底物銠催化條件下的環化反應 15
2.3三環α-ketocyclopropylnitrile在電子作用下的開環反應研究 7
2.4 結論 22
第三節 實驗 23
3.1 一般實驗方法 23
3.2 實驗研究及方法與光譜資料 24
參考文獻 63
化合物光譜目錄 65

參考文獻
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