此論文描述以鎳或鈷金屬在有機合成上，以偶合反應來形成雜環或環化反應，總共分成三個部分，四個章節。第一章是以鎳金屬催化鄰碘苯酯與oxabenzonorbornadiene衍生物進行反應，得到一系列具有不錯產率的苯環香豆素。此外，在同一章節裡，以相同反應條件也可以延伸進行分子間的環化反應。第二章與第三章裡，則是談論有關於鎳與鈷金屬催化碘烷化合物與易反應的烯類，進行還原偶合反應得到具有長碳鍊的有機化合物。第四章是以鄰碘苯醛或鄰碘苯酮為起使物，在鎳金屬的催化下得到具有多環的有機酮化合物，其反應機構包含了□-烷基的離去過程。
第一章以鎳金屬催化製備香豆素，香豆素可以應用在藥物合成的前驅物，或是應用在有機發光材料領域。以鄰碘苯酯與與oxabenzonorbornadiene衍生物在鎳金屬的催化下進行反應，可以合成出一系列具有高產率的苯環香豆素。
在此反應條件下，可以藉由鎳金屬催化合成具有各種不同官能基的苯環香豆素。 此反應機構已被發表研究，我們也嘗試著進一步合成出內醯胺化合物。
在相同的鎳金屬催化條件下，起使物改成鄰碘苯胺亦可進行分子間環化反應得到具有不錯產率的內醯胺化合物。
第二章討論的主題，是以鎳金屬催化飽和碘烷化合物與具有拉電子基的烯類進行偶合反應，得到還原飽和且產率相當不錯的偶合產物。
此反應包含許多種類的一級、二級、三級碘烷或溴烷化合物，與反應活性高的烯類，如：共軛烯酯，共軛烯酮或醯胺類，可以得到飽和長碳鍊的偶合產物。
第三章則以鈷金屬催化鹵烷基化合物與與具有拉電子基的烯類進行偶合反應，得到還原飽和且產率相當不錯的偶合產物。此反應中間體是經由氧化加成而非形成自由基來完成反應。第四章是鎳金屬催化鄰碘苯醛或鄰碘苯酮與烯類進行偶合反應，得到多元環的有機酮化合物。
與之前研究不同的是，就算以鄰碘苯酮為起使物，其產物依舊是有機酮類而非有機醇類。這種結果我們推論是經由□-烷基離去的步驟，此種過程在鎳金屬的催化中未曾發現，藉由分離反應中的副產物可以對反應機構有更進一步的瞭解。

The thesis describes nickel and cobalt-catalysed organic synthesis leading to couplings, carbocyclisations and formation of heterocyclic compounds. It is subdivided into three broad topics, spread out into a total of four chapters. The first chapter describes nickel-catalysed cyclisation of □-iodo-(z)-propenoates with oxabenzonorbornadiene derivatives resulting in the formation of benzocoumarins in good yields. An extension of the same methodology to reveal intramolecular cyclisation has also been described subsequently in the same chapter. The second and third chapters deal with reaction of saturated alkyl halides with reactive alkenes to form reductive coupling products in the presence of nickel and cobalt complexes. The fourth chapter consists of carbocyclisation of ortho-iodobenzaldehydes and ketones to give rise to polycyclic ketones in the presence of nickel complexes. The latter also includes an unusual □-alkyl elimination mechanism.
The first chapter details a nickel-catalysed strategy to prepare coumarins which are well known drug precursors and excellent materials for OLED (organic light emitting devices). Treatment of o-iodoesters with oxabenzonorbornadiene derivatives in the presence of nickel complex, led to the synthesis of benzocoumarins in good to excellent yields. The methodology developed by us can be utilized for the preparation of a variety of substituted coumarin derivatives by simple and efficient utilization of nickel catalysis. The mechanism of this interesting reaction has also been discussed. The later part of the same chapter recounts the extension of the methodology to prepare lactams. When an ortho-iodoamide is subjected to the same nickel-catalysed reaction conditons, intramolecular Heck-type cyclisation occurred to form lactams in good yields. The lactam framework synthesized by this methodology is contained in many naturally occurring compounds e.g. Oxychelerythrine, Oxyavicine etc.
The second chapter describes reaction of sp3 alkyl halides with electron withdrawing alkenes in the presence of nickel complex to give rise to reductively coupled products. The strategy encompasses a variety of primary, secondary and tertiary alkyl halides and bromides, which react with various activated olefins e.g. □□□-unsaturated esters, ketones, nitriles etc. to form saturated products in good to excellent yields. An extension of this reductive coupling methodology to oxabenzonorbornadienes has been depicted in a later part of the same chapter. Ring opening of oxabenzonorbornadienes to form substituted dihydronaphthol derivatives in the presence of nickel complexes is delineated in the final portions of the second chapter.
The third chapter recounts cobalt-catalysed reductive coupling of saturated alkyl halides with electron withdrawing alkenes to form saturated products. The cobalt-mediated reductive couplings are the first reports of such utilization of cobalt complexes. The mechanism of this reaction has been extensively explained. Mechanistically, the reaction appears quite different from the previously reported similar couplings, as evinced by the various experiments that were performed. The reasons for why the reaction may be an oxidative addition driven one rather than a radical mediated one, have been put forward.
The fourth chapter depicts the reaction of ortho-substituted iodobenzaldehydes and ketones with bicyclic alkene derivatives in the presence of nickel complexes to form annulated ketones. The first part of the chapter describes the reaction of o-iodobenzaldehydes with various bicyclic alkenes in the presence of nickel catalyst to form polycyclic ketones in good yields. In the second portion of this chapter, there is a description of the use of o-iodoketones with the same bicyclic alkenes to form similar polycyclic ketone products. It is surprising to note that when o-iodoaldehydes were replaced by o-iodoketones the products of the reaction were still the same i.e. ketones, although based on precedents, the expected products should have been cyclic tertiary alcohols. This bizarre behavior was investigated in detail by postulating unprecedented □-alkyl elimination during the reaction. Such □-carbon elimination is yet unknown in nickel-catalysed systems. Also, the fate of the moiety fractionated from the starting ketone compound was determined by isolating a key side product, leading to a better understanding of the mechanism of this reaction.

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