摘要
藉由鉑、銠、金錯合物和氯化碘來居間催化 烯炔分子的分子內環化來合成螺旋的三烯酮類分子，而且發生在期間的重排反應再本論文中一起被探討。 第一章節解釋利用氯化鉑(5mol%)催化而產生Bergman的環化在不同的烯二炔分子而進行Bergmann的環化反應而得到高產率稠環的環戊基萘分子。拉電子基與推電子基對於反應過程有深遠的影響，而且它可以簡單的闡述在利用不同的烯二炔分子下。其反應的機構被推測出經過 Pt-π-alkyne 的中間體。 第二章致力於利用TpRuPPh3(CH3CN)2PF6(10mole%)來催化芳香族的烯二炔類分子經由高立體選擇性的分子內親核加成在π-alkyne的官能基上。這種環化適用於分子內與分子間兩種模式，然後簡單的去製備這類型芳香族的官能基包含O、N等異原子。經由這系列的實驗結果,，ㄧ個鑲入或是加成的反應機構被推導出來。 第三章利用5mole%的AuClPEt3/H2O2 和 PtCl2/CO/H2O 的催化劑來氧化環化2-Ethenyl-1-(prop- 2’-yn-1’-ol)benzenes 得到萘衍生物的醛類或酮類化合物。 。金的催化劑系統被發現優於鉑，因為主要產物醛或酮的產率較優從不同的醇類試劑中。末端炔類得到醛而雙取代炔類得到酮且皆有很高產率。經由三圓環的研究建立碳陰離子中間物在這類反應過程中。 最後一章探討關於合成螺旋〔4，5〕的三烯酮 從4′-Methoxy-2-phenylethnyl-biphenyls 藉由氯化碘分子內Ipso- halocyclization引導和酸的居間重排。其Ipso- halocyclization關鍵在於甲氧基若是在四號位置，若是甲氧基不是在四號位置，則試劑無法形成螺旋狀化合物，而得到碘基菲，一個酸居間的反應機構被推導出來。碘基菲可被準備用於其他Pd(鈀)金屬催化劑的催化反應起始物例如 Heck reaction。
並列摘要
Intramolecular cyclization of ene-ynes catalyzed by platinum, ruthenium and gold complexes, Synthesis of polyarenes via electrocyclization are dealt in this thesis. The thesis consists of four chapters The first chapter explains Bergman cyclization of a variety of enediynes by catalytic platinum chloride (5 mol%) to give a cyclopentyl fused naphthalene rings in high yields. The presence of electron withdrawing and donating groups has a dramatic influence on the course of the reaction and it is very well demonstrated using different enediynes. The reaction mechanism has been proposed to involve the platinum π- alkyne intermediate. The second chapter deals with aromatization of enediynes via highly regioselective intramolecular nucleophilic additions on π- alkyne functionality using TpRuPPh3(CH3CN)2PF6 (10 mol%). This cyclization works for both inter and intramolecular modes, thus allowing an easy access to prepare functionalized aromatic compounds containing O, N heteroatoms. An addition/insertion mechanism is proposed based on the results of a series of experiments. The third chapter presents the oxidative cyclization of 2-ethenyl-1-(prop-2′-yn-1′-ol)benzenes to naphthyl aldehydes and ketones via catalytic oxidative cyclization using 5 mol% of AuClPEt3/H2O2. Gold-catalyst has found to be effective for the production of the desired ketones and aldehydes from diverse alcohol substrates. Terminal alkynes gave the aldehydes, and the internal alkynes gave the ketones in high yields. The final chapter discusses about the synthesis of spiro[4.5]trienones from 4′-methoxy -2-phenylethnyl-biphenyls by intramolecular Ipso- halocyclization induced by ICl and their acid mediated rearrangement. The key in ipso-halocyclization is the presence of the methoxy group at 4′ position. In presence of methoxy group at a position other than 4′, substrates failed to give the spiro compound, instead they gave iodophenanthrenes. An acid mediated mechanism was proposed for rearrangement. Iodophenanthrenes prepared were used as starting materials for other palladium assisted catalytic reactions like Heck coupling reaction.
參考文獻
延伸閱讀
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