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Author: 林亞萱
Lin, Ya-Syuan
Thesis Title: 一價銠金屬催化苯並環丁醇具位向選擇之開環反應及其接續與馬來醯亞胺之共軛加成反應
Rhodium(I)-Catalyzed Regioselective Ring Opening of Benzocyclobutenol and Subsequent Conjugate Addition Reaction with Maleimides
Advisor: 吳學亮
Wu, Hsyueh-Liang
Degree: 碩士
Master
Department: 化學系
Department of Chemistry
Thesis Publication Year: 2016
Academic Year: 104
Language: 中文
Number of pages: 252
Keywords (in Chinese): 銠金屬催化苯並環丁醇共軛加成馬來醯亞胺
Keywords (in English): rhodium(I)-catalysted, benzocyclobutenol, conjugate Addition, maleimide
DOI URL: https://doi.org/10.6345/NTNU202204536
Thesis Type: Academic thesis/ dissertation
Reference times: Clicks: 140Downloads: 0
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  • 本篇論文探討利用Rh(I)銠金屬催化劑催化苯並環丁醇36進行選擇性斷C(sp2)‐C(sp3)鍵隨後再和馬來醯亞胺51進行反應。在0.015莫耳的銠金屬[Rh(cod)(OH)]2催化劑催化苯並環丁醇36進行位置選擇性開環,中間體芳基銠金屬化合物再和馬來醯亞胺進行共軛加成反應最後和酮基進行醛醇反應。生成主要產物化合物52具有六員環與五員環順式相駢的結構,且羥基的位向與橋頭氫原子為順式的關係;反之另一次要非鏡像異構物53,羥基與橋頭氫原子則為反式關係。另有單離得到次要化合物54,則為單進行共軛加成反應,沒有進行醛醇反應的產物。

    This thesis describes the employment of [Rh(cod)(OH)]2 as a catalyst in the site-selective cleavage of C(sp2)‐C(sp3) the bond of benzocyclobutenols 36 and their subsequent reaction with maleimides 51. In the presence of 1.5 mol% of [Rh(cod)(OH)]2, ring-opening reaction of benzocyclobutenols 36 proceed in a regioselective manner, allowing a two-step reaction involving a conjugation addition reaction of the thus-obtained Ar-Rh species with maleimides 45 and an aldol reacton with the resulting ketone group. The major products 52 consist of cis-fused 6-membered and 5-membered rings with the stereochemistry of hydroxyl group cis to the bridged head H-atoms, whereas the hydroxyl group is trans to bridged head H-atoms in the minor diastereomers 53. The intermediate 54, resulting from the initial conjugated addition of Ar-Rh to 45, was isolated as the minor product.

    目錄 中文摘要 英文摘要 圖目錄 表目錄 式目錄 謝誌 英文縮寫對照表 第一章 緒論 1 第二章 文獻回顧 3 第三章 實驗結果與討論 25 第四章 合成應用 47 第五章 結論 50 第六章 實驗部分 51 第七章 參考文獻 113 附錄 116 X‐ray ORTEP 解析圖譜及數據 117 1H及13C之NMR光譜圖 136

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