姚清發Yao, Ching-Fa吉旺SHINDE JIVAN SARJERAO2024-12-172024-01-132024https://etds.lib.ntnu.edu.tw/thesis/detail/8da0b153f80de01a32e021a4de5e0cc1/http://rportal.lib.ntnu.edu.tw/handle/20.500.12235/123381鈀金屬催化末端炔基芳基化與銅金屬催化非對稱尿素合成生物學相關雜環的策略本論文的內容分為五個章節（A、B、C、D和E）A章節分為四個部分。第一部分介紹了使用苯硼酸的過渡金屬催化氫芳基化反應對炔烴的應用。接下來，第二部分聚焦於以Rh和Ni催化劑進行的氫芳基化反應的先前報告和深度分析。下一部分描述了二酮化合物的末端炔烴的鈀（II）催化C-C鍵結和環化反應。此外，最後一部分介紹並合成了從次級胺和醯胺疊氮化物中使用銅催化劑合成非對稱脲。B章節中描述了鈀催化下芳基硼酸對1,3-二酮化合物末端炔烴的對位選擇性（Markovnikov's）加成，且進一步描述了1,3-二羰基烯烴在三取代的6 元吡喃環上的應用，以及（E )-4-亞甲基-1,6-二苯基己-5-en-1-酮合成，並詳細討論了機制研究。 C章節中包含了從吲哚/胺和苯甲醯疊氮化物中使用銅催化進行更環保、溫和和高效的非對稱脲衍生物的合成。也可應用在多種吲哚衍生物、胺和苯甲醯疊氮化物底物，具有良好的官基容忍性。且透過機制和表徵數據研究了雙吲哚對苯甲酰疊氮化物的反應性和克級尿素合成。 D章節重點在於「在無需定向基下透過鈀(II)催化末端炔烴的區域選擇性氫芳基化：烯基、同烯丙基和1,3-二烯體系的合成。」文中描述了對機制的詳細研究，包括對照實驗和特性數據 E章節中描述了鈀(II)催化硼酸與苯甲酰胺、磺酰胺和吲哚的炔丙基加成合成烯丙胺和烯胺，並提供了反應機理研究的進一步理論計算和表徵數據。Palladium(II)-Catalyzed Arylation of terminal alkyne and Cu-Catalyzed Unsymmetrical Urea Strategies for the Synthesis of Biologically Relevant HeterocyclesThe contents of this dissertation are divided into five chapters (A, B, C, D& E). Chapter [A] is subdivided into four parts. Part one is the introduction of transition metal catalyzed hydroarylation of alkyne by using phenyl boronic acid. Next, second part is focusing on a previous report and depth analysis of hydroarylation reaction using Rh and Ni catalyst. Next part is a palladium (II) catalyzed C-C coupling and cyclization reaction of terminal alkyne of dicarbonyl compound. The last part is the introduction and synthesis of unsymmetrical urea from sec. amine and acyl azide by using Cu-catalyst.Chapter [B] in this chapter main focus on palladium-catalyzed regioselective(Markovnikov's) addition of aryl boronic acid to terminal alkyne of 1,3-dicarbonyl compounds is described further application of 1,3-dicarbonyl alkene for trisubstituted 6-membered pyran ring and (E)-4-methylene-1,6-diphenylhex-5-en-1-one synthesis with details discussion of mechanistic study described. Chapter [C] this chapter contains Cu-catalyzed greener, mild and efficient unsymmetrical urea derivatives synthesis from indole/amine and benzoyl azide. A number of indole derivatives, amines and benzoyl azide substrates were successfully employed with good functional group tolerance. Reactivity of bis indole towards benzoyl azide and gram scale urea synthesis were investigated with mechanism and characterization data.Chapter [D] was emphasis“Palladium (II)-Catalyzed Regioselective Hydroarylation/Hydroalkenylation of Terminal Alkynes via Carbopalladation without a Directing Group: Synthesis of Allylic, Homoallylic and 1,3-Diene Systems” The details of mechanistic study with control experiment and characterization data described.Chapter [E] in this part palladium (II)-catalyzed addition of boronic acid to propargylic alkyne of benzamide, sulfonamide and indole for allylic amide and amine synthesis described and further theoretical calculations for the reaction mechanism studies presented with characterization data.鈀(II)催化劑對位選擇性加成炔基13-二酮炔13-二酮烯吡喃去苯甲 醯炔基苯醚炔基N -甲基苯胺炔基N-甲基磺胺炔基N-甲基苯甲醯胺N-炔基吲哚乙酸鉀銅碘吲哚苯胺雙吲哚苯甲醯疊氮化物脲乙酸乙酯Palladium (II) catalystRegioselective additionPropargylic 13 dicarbonyl alkyne13 dicarbonyl alkenePyranDebenzoylationPropargylic Phenyl EtherPropargylic N-methyl Phenyl AminePropargylic N-methyl sulfonamidePropargylic N-methyl benzamideN-Propargylic indolePotassium AcetateCopper iodideIndoleAnilinebisIndolebenzoyl azideUreaEthyl Acetate學術論文