臺灣博碩士論文加值系統

Ⅰ. 利用雜環 [6+3] 環化加成反應合成11-氧代類固醇的研究
富烯的環化加成反應(例如 [4+3], [2+2], [4+2], [6+4], [6+2]等)，提供了合成各種多元環化合物，一個便捷而有效的途徑。 一般而言，當富烯與1,4-benzoquinone 反應時，通常會得到 [4+2] 環化加成產物。 但是，我們發現，將6-dimethylaminofulvene和1,4-benzoquinone 反應時，卻得到 oxatricyclic 的雜環 [6+3] 環化加成產物。 這是經由雜環 [6+3] 環化加成反應來合成 3-oxa-bicyclo[4.3.0]nonane 系統化合物的第一個例子。
此外，這一種雜環 [6+3] 環化加成反應，也為 11-氧代類固醇的合成，開啟了另一個快速的合成途徑。
Ⅱ. 1,3-二羰基化合物與二環戊二烯或簡菠烯的氧化加成反應
近年來，有許多研究利用 cerium(IV) ammonium nitrate (CAN)，將 1,3-二羰基化合物到氧化加成各種烯類的反應被報
導。 另一方面， Tricyclo[5.2.1.02,6]decane 系統曾被發現存在於已知的天然物中，同時也是合成各種天然和非天然化合物的一個重要中間產物。
因此，本研究嘗試著經由CAN的作用，將 1,3-二羰基化合物氧化加成至二環戊二烯，試著合成烷基化的 Tricyclo[5.2.1.02,6]decane nitrate，並且嘗試將1,3-二羰基化合物與簡菠烯及其衍生物進行氧化加成反應。

Part I: Facile synthesis of 11-oxasteroid via the hetero [6+3] cycloaddition
Cycloadditions of fulvenes (e.g.[4+3], [2+2], [4+2], [6+4], [6+2]) provide general and powerful approaches to various polycyclic systems and natural products. Fulvenes usually react with benzoquinones to give the [4+2] cyclo-addition adducts. In contrast, we have found that reaction of the 6-dimethylaminofulvene and benzoquinone results in the formation of the oxatricyclic product. This is the first example of the synthesis of 3-oxa-bicyclo[4.3.0]nonane system via the hetero [6+3] approach.
Part II: Oxidative addition of 1,3-dicarbonyl compounds to dicyclopentadiene and norbornene
Recently, cerium(IV) ammonium nitrate (CAN)-mediated addition of 1,3-dicarbonyl compounds to various alkenes was reported to exploit its synthetic potential. Tricyclo[5.2.1.02,6]decane system is a useful building block for the synthesis of natural and unnatural compounds. As the result, we decide to study the 1,3-dicarbonyl addition to endo-dicyclopentadiene and norbornene mediated by CAN.

中文摘要************************...i
英文摘要************************ii
目錄**************************iii
圖目錄*************************v
表目錄*************************vi
附圖目錄************************vii
第一章 經由雜環 [6+3] 環化加成反應合成11-氧代類固醇骨架
的研究*********************.1
1.1 緒論***********************.1
1.2 結果與討論********************12
第二章 1,3-二羰基化合物與二環戊二烯或簡菠烯進行氧化加成反
應的研究********************22
2.1 緒論***********************22
2.2 結果與討論********************28
第三章 實驗部分及光譜數據***************.33
3.1 實驗儀器*********************33
3. 2一般實驗方法*******************.34
3.3 富烯的雜環 [6+3] 環化加成反應**********.35
3.4 1,3-二羰基化合物與二環戊二烯的氧化加成反應****51
3.5 1,3-二羰基化合物與簡菠烯的氧化加成反應******63
參考文獻************************67
附圖**************************72
附錄*************************.193

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