臺灣博碩士論文加值系統

芳香烴化合物或是環庚三烯與六羰鉻錯合後，可得到穩定的（6-芳香烴）或（6-環庚三烯）三羰鉻錯合物。藉由三羰鉻的拉電子效應，降低了環上的電子密度，改變了苯環或是環庚三烯的反應性質。我們藉由此特性來探討芳香烴三羰鉻錯合物與矽親核性試劑的反應性，以及利用三羰鉻錯合物來製備帶有長鏈醛基之環庚三烯衍生物，並研究其衍生物以鎳金屬催化下，是否可進行分子內環化反應。
有機矽陰離子與三羰鉻錯合物進行親核性加成或取代反應，再以三氟醋酸或Davis reagent終止反應，可得到環己二烯具有矽官能基取代的產物，或維持三羰鉻錯合物結構的有機矽化物。此外，（6-環庚三烯）三羰鉻錯合物也可與矽陰離子進行親核性加成反應，以三氟醋酸終止反應後，可得到環庚二烯的有機矽化物。
（7-環庚三烯基）三羰鉻陽離子錯鹽與帶有氰基之有機鋅銅試劑反應，生成7-exo-取代的（6-環庚-1,3,5-三烯）三羰鉻錯合物。再以氧化劑將三羰鉻錯合物去錯合，並將氰基還原為醛基，將此環庚三烯側鏈帶醛基的化合物與Et3SiH及催化量的PPh3、Ni(cod)2作用，可進行分子內環化反應，產生並環雙環或是三環的化合物。

Complexation of arenes with Cr(CO)6 produced stable (6-arene)Cr(CO)3 complexes in good yields. The addition reaction of lithiophenyldimethylsilane with (6-arene)Cr(CO)3 complexs afforded cyclohexa-1,3-dienes containing the silyl group after quenching reaction intermediates with CF3COOH. Treatment of the same reaction intermediates with the Davis reagent gave the silyl-substituted (6-arene)Cr(CO)3 complexs. Moreover, the same reaction pattern was observed with (6-cyclohepta-1,3,5-triene)Cr(CO)3 complexs. Thus, nucleophilic addition of LiSiMe2Ph to (6-cyclohepta-1,3,5-triene)Cr(CO)3 complexes produced the silyl-substituted cyclohepta-1,3-diene derivatives after acid quench.
The addition of cyano-functionalized zinc-copper reagents NC(CH2)nCu(CN)ZnI to (tropylium)Cr(CO)3 cation gives (6-cyclohepta-1,3,5-triene)Cr(CO)3 complex with a cyano-functionalized side-chain at C-7 position of the ring. Decomplexation of the Cr(CO)3 moiety followed by reduction of the cyano group with diisobutylaluminum hydride afforded cyclohepta-1,3,5-triene derivatives containing an aldehyde side-chain at C-7 posotion of the ring. Intramolecular cyclization of the aldehyde-substituted cyclohepta-1,3,5-trienes using 5 molar equiv of Et3SiH and catalytic amount of PPh3 and Ni(cod)2 afforded fused bicyclic or tricyclic compounds.

目錄 .. i
中文摘要 . iii
英文摘要 . iv
第一章 緒論 1
第二章 （6-芳香烴）及（6-環庚三烯）三羰鉻錯合物與矽親核試劑
之加成反應
2.1 前言
2.1.1三羰鉻錯合物與親核性試劑的反應 . 15
2.1.2矽陰離子在有機合成的應用 . 18
2.1.3 (±)-trans-2-(phenylsulfonyl)-3-aryloxziridine (Davis reagent)
在有機合成的應用 . 27
2.2結果與討論
2.2.1（6-芳香烴）三羰鉻錯合物與矽親核試劑之加成反應 .32
2.2.2（6-環庚三烯）三羰鉻錯合物與矽親核試劑之加成反應 .. 39
2.3結論 41
第三章 帶有醛基之環庚三烯衍生物利用鎳金屬催化進行
分子內環化反應之研究
3.1前言
3.1.1環庚三烯衍生物在有機合成上的應用 .. 43
3.1.2 利用過渡金屬催化劑來進行分子間或分子內環化反應 48
3.2結果與討論
3.2.1帶有長鏈醛官能基之環庚三烯化合物以鎳金屬催化的
.分子內環化反應 .57
3.2.2帶有苯甲醛官能基之環庚三烯化合物以鎳金屬催化的
.分子內環化反應 .. 64
3.3結論 68
第四章 實驗部分
4.1 分析儀器及基本實驗操作 .. 69
4.2 實驗部分及光譜數據
4.2.1 一般實驗程序 71
4.2.2 三羰鉻錯合物與矽親核性試劑的加成反應 72
4.2.3 C-7位置帶長鏈官能基之環庚三烯分子內環化反應 78
第五章 參考文獻 93
附圖 99

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