本論文分為三個章節，主要是利用過渡金屬催化或促進烯炔類化合物進行環化反應。
第一章主要是探討是利用鈷金屬錯合物促進順式環氧烯炔類化合物進行
環化加成反應。當順式環氧烯炔基化合物和 Co2(CO)8 在充入的一氧化碳可得到三環δ-內酯化合物，在此反應中可能經由 [5+1]/[2+2+1] 或 [5+1]/[2+2] 環化加成反應的過程這兩種過程取決於配位基的結構和反應條件。我們所推測的反應機構包含鈷金屬配位到環狀丙二烯上。本反應除了可以架構含碳的三環化合物，還可以引進含氧、氮等異原子，表示此反應具有不錯的官能基容忍度，這在合成複雜的多環分子上具有極高的應用價值。
第二章主要是探討研究釕金屬錯合物 TpRuPPh3(CH3CN)2PF6 催化烯二炔類進行親核性加成之芳香化反應，此反應具有極高的位向選擇性，親核性試劑只會加成在多電子的炔基上，且多種溫和的親核性試劑皆可反應，如水、醇類、苯胺、醛類和酯類等，這些親核性試劑則會加成至芳香環上，可應用於不同官能基芳香環衍生物的合成上。此外，我們也發現當苯環上有推電子基時，反應性會增加，從同位素實驗中可以證明其反應機構是經由 ruthenium-π-alkyne 而非釕金屬亞乙烯基。
第三章主要是探討利用釕金屬錯合物 TpRuPPh3(CH3CN)2PF6 催化烯炔類化合物進行環化反應，而形成環戊二烯類衍生物。此外，當釕金屬錯合物為 TpRuPPh3(CH3CN)2SbF6 在催化 1-alkyl-2-ethynyl benzene 化合物形成1-alkyl-1H-indene時，催化效果比 TpRuPPh3(CH3CN)2PF6 效率更好。此反應的機構經由重氫取代實驗證明包含經由釕金屬亞乙烯基中間物的 [1,5]-sigmatropic 氫轉移。另外，我們也發現當 cis-2-en-4-yn-1-ol 在 TBS 保護下經由釕金屬錯合物 TpRuPPh3(CH3CN)2PF6 催化下亦可得到不錯產率的環戊酮衍生物。

Arjan Viram Odedra, Ph.D., National Tsing Hua University, June 2006. Cobalt and Ruthenium Complexes Mediated/Catalyzed Intramolecular Cyclization of Enynes. Advisor: Professor Rai-Shung Liu

Intramolecular cyclizations of enynes mediated/catalyzed by cobalt and ruthenium complexes are described in this dissertation. The thesis is divided into three chapters.
First chapter presents cobalt mediated double carbonylative cycloaddition of epoxy alkyne with tethered alkyne. In the presence of Co2(CO)8 and CO, cis-epoxyalkynes bearing a tether olefin undergo a tandem [5 + 1]/[2 + 2 + 1] and/or [5 + 1]/[2 + 2]-cycloaddition depending on substrate and condition. In this novel cycloaddition reaction cobalt stitches together cis-epoxy alkyne, CO and olefin in highly stereocontrolled way to synthesize tricyclic -lactones efficiently in a one-pot operation. The reaction mechanism is proposed to involve a cobalt-coordinated cyclic allene species. This new approach is successfully extended to construct various tricyclic carbo- and heterocyclic frameworks that can tolerate suitable oxygen and nitrogen functionalities.
Second chapter deals with ruthenium catalyzed anionic bergman cyclization of unstrained enediynes. TpRu(PPh3)(CH3CN)2PF6 (10 mol%) catalyst effected the nucleophilic addition of water, alcohols, aniline, acetylacetone, and dimethyl malonate to unfunctionalized enediynes under suitable conditions (100 oC, 12-24 h), and gave functionalized benzene products in good yields. In this novel cyclization, nucleophiles very regioselectively attack the internal C1’-alkyne carbon of enediynes to give benzene derivatives as a single regioisomer. Experiments with methoxy substituents exclude the possible involvement of naphthyl cations as reaction intermediates in the cyclization of (o-ethynylphenyl) alkynes. Deuterium-labeling experiments indicate that the catalytically active species is ruthenium-□-alkyne rather than ruthenium-vinylidene species. This hypothesis is further confirmed by the aromatization of o-(2’-iodoethynyl)phenyl alkynes with alcohols. We propose a nucleophilic addition/insertion mechanism for this nucleophilic aromatization based on a series of experiments.
Last chapter discusses ruthenium catalyzed cycloisomerization of enenye. TpRuPPh3(CH3CN)2PF6 (10 mol %) catalyzed the cycloisomerization of unactivated cis-3-en-1-ynes and efficiently produces stable cyclopentadiene and related derivatives. TpRuPPh3(CH3CN)2SbF6 catalyzed cycloisomerization of 1-alkyl-2-ethynyl benzene to 1-alkyl-1H-indene in excellent yield whereas TpRuPPh3(CH3CN)2PF6 was inactive. The mechanism of this cyclization is proposed to involve a [1, 5]-sigmatropic hydrogen shift of ruthenium-vinylidene intermediates on the basis of deuterium labeling experiments. TpRuPPh3(CH3CN)2PF6 also catalyzed isomerization of TBS-protected cis-2-en-4-yn-1-ol to afford cyclopentenone derivatives in good yield.

Chapter 1
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