臺灣博碩士論文加值系統

本論文著重探討acceptor/acceptor-型重氮底物與苯類化合物在不同條件下的反應；內容分為兩個部分。
在論文的第一章，我們首先描述了重氮丙二酸酯 (diazomalonates) 與苯300 nm的光照反應條件下生成具有bicyclo [3.2.0] hepta-2,6-diene骨架的2,6-雙酯化合物。根據實驗結果，我們推測此產物應是由cycloheptatriene中間體經過連續1,5-酯基遷移(1,5-carboxylate migration)和[2 + 2] 環化加成(cycloaddition)的過程而產生。我們進一步發現此反應還可應用於α-diazo-α-phosphorylacetate型的底物；以中等產率得到2-phosphoryl-6-carboxylate-bicyclo[3.2.0] hepta-2,6-diene類化合物 (式I)。
α-Diazocarbonyl底物與苯類化合物在過渡金屬催化條件下，可進行aromatic substitution或aromatic cycloaddtion兩種反應。而diazo碳上的取代基對控制這兩種反應路徑有著重要的影響。在本文的第二章，我們描述將此策略應用到biphenyl α-diazoketone體系中；研究 diazo碳上的取代基與反應選擇性(chemoselectivity)之間的關係。選用的取代基包括α-乙醯基(acetyl)，α-乙酯基(ethyl carboxylate)和α-苯甲醯基(benzoyl)。在Rh2(OAc)4或Rh2(oct)4的催化條件下，我們首先發現絕大多數具有α-乙醯基的底物可選擇性地進行aromatic substitution反應；產生 phenanthrol 類化合物。與此相比，α-乙酯基取代的類似物則在兩種反應間表現出較差的選擇性。除了phenanthrols之外，其反應還給出了由aromatic cycloaddtion所形成的benz[α]azulenone衍生物。而互為競爭的兩條反應路徑中，α-苯甲醯基取代的底物仍表現出對aromatic substitution極高的選擇性。除了產生phenanthrol之外，我們驚奇地發現在反應中還生成2-(biphenyl-2-yl)-1-phenyl-ethan-1-one和 1-([1,1′-biphenyl]2-yl)-2-phenylethane-1,2-dione；而後者則是在diazo底物的催化反應中首次被發現(式II)。

The dissertation involves exploring the new reactions of acceptor/acceptor-type diazo substrates with phenyl compounds. The related contents are divided into two chapters.
In Chapter one, we disclose a photo-induced decomposition of diazomalonates in benzene. Upon the irradiation with 300 nm UV light, the reaction unexpectedly gives the formation of 2,6-dicarboxylate bicyclo[3.2.0]hepta-2,6-dienes. Based on the mechanistic studies, we propose that these products may be derived from cyclohepta-1,3,5-triene intermediates via a tandem 1,5-carboxylate migration/[2 + 2] cycloaddition sequence. Besides, the protocol is applicable to α-diazo-α-phosphorylacetates, in affording 2-phosphoryl-6-carboxylate-bicyclo[3.2.0] hepta-2,6-dienes in moderate yields (Scheme I).
Transition-metal-catalyzed intramolecular aromatic cycloaddition or aromatic substitution reactions of α-diazocarbonyl compounds are widely employed for the construction of unsaturated polycycles. Recently, we attempted these reactions to the biphenyl α-diazoketones that contain the different electron-withdrawing substitutents (EWG = COCH3, CO2Et, COPh) on the diazo carbon, as a means of probing the substitution effect on the chemoselectivity (Scheme II). Upon exposure to catalytic Rh2(OAc)4 or Rh2(oct)4, most of the α-acetyl substituted substrates are found to strictly follow an aromatic substitution pathway in the carbenoid-mediated cyclization, to allow the exclusive generation of phenanthrol derivatives. As a comparison, the carboxylate substituted analogues produce the mixtures phenanthrols and benz[α]azulenones under the same catalytic conditions, revealing their lower differentiation ability between the two competing processes. Moreover, high chemoselectivity for aromatic substitution over cycloaddition is observed for the substrates bearing the α-benzoyl group. Surprisingly, in addition to offering phenanthrols, the reaction also produce 2-(biphenyl-2-yl)-1-phenyl-ethan-1-one and 1-([1,1′-biphenyl]2-yl)-2-phenylethane-1,2-dione. The latter one has been regarded as an unprecedented product obtained with diazo precursors. The results from these experiments are discussed in Chapter 2.

中文摘要......i
英文摘要......iii
謝誌..........v
目錄..........vi
縮寫符號對照表.viii
第一章 α-Diazoacetates與苯之光照反應......1
第一節 緒論..............................1
第二節 結果與討論.........................4
第三節 結論..............................13
第四節 實驗..............................14
4.1 一般實驗方法.........................14
4.2 實驗步驟及光譜數據....................16
參考文獻.................................28
附錄一 化合物光譜圖.......................30
化合物光譜目錄............................31


第二章 α-取代基對biphenyl α-diazoketone Rh(II)-催化分子內環化反應選擇性之影響...................................97
第一節 緒論..............................97
第二節 結果與討論........................102
第三節 結論.............................110
第四節 實驗.............................111
4.1 一般實驗方法........................111
4.2 實驗步驟及光譜數據...................111
參考文獻................................133
附錄二 化合物光譜圖......................137
化合物光譜目錄..........................138

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