釕金屬錯合物誘發丙炔基吡咯之環化及鄰位羰基芳香炔之環化及二聚反應

Cyclization/Dmierization Reactions of Ruthenium Complex with Substituted N-Propargyl Pyrroles and Aryl Alkynes Containing o-Carbonyl Group

賈丕業(Pi-Yeh Chia)

指導教授 ： 林英智

國立臺灣大學/理學院/化學研究所/博士(2016年)

https://doi.org/10.6342/NTU201900725

摘要

第一章：利用釕金屬錯合物[RuCp(PPh3)2Cl]，與N-炔丙基吡咯有機化合物1a反應，形成釕金屬亞乙烯基錯合物2a，將錯合物2a溶於二氯甲烷中，與溶在甲醇中的氨進行反應，可得到釕金屬費雪型胺基碳烯錯合物5a；然而利用一級氨在相同的反應環境下與錯合物2a反應，則可得到環化後的釕金屬碳烯錯合物8a。利用鹼與錯合物2a反應可得到去質子化後的中性的釕金屬乙炔基錯化合物3a，錯合物3a與烷化試劑反應可得雙取代的亞乙烯基錯合物4a-b，之後利用鹼再進行分子內的環化反應可得到釕金屬含雜環呋喃的錯化合物6a-b，其中6a錯化合物則會伴隨著[1,3]苄基轉移，而得到釕金屬錯合物7a。利用釕金屬錯合物[RuCp(PPh3)2Cl]與含吡咯苯甲基乙炔有機化合物9在二氯甲烷中反應，可得到釕金屬亞乙烯基錯化合物10，當溶劑改變為甲醇時，則會得到具七環雙取代的釕金屬亞乙烯基錯化合物11，而其環化過程中可能會先形成錯合物10。亞胺烯炔有機物12與釕金屬錯合物[RuCp(PPh3)2Cl]在二氯甲烷中反應，則可得到具六環帶正電亞胺離子的釕金屬錯合物。
第二章：釕金屬亞乙烯基錯化合物2a，利用分子間脫水之碳碳耦合反應，形成了雙核雙亞乙烯基的錯化合物4a；錯合物2a具有1-羥基茚這樣骨架，是由釕金屬錯合物[Ru]-Cl ([Ru] = Cp(PPh3)2Ru) 與1a 鄰-丙炔苯甲醛 進行環化反應而成，與1a相似在苯環位置修飾1,3 –二氧戊環的苯甲醛1b ，也可以透過上面所提到的反應流程，獲得雙核雙亞乙烯基的錯化合物4b。然而，當改使用修飾氟原子於苯環上的1c，似乎就限制雙核耦合反應，只僅單純得到環化後的2錯化合物。將具有酮基這樣官能基的1f、1g和1h於分別甲醇中與[Ru]-Cl反應，都能分別得到環化後的釕金屬亞乙烯基錯化合物2f、2g和2h ；但前面所提到分子間雙金屬耦合反應卻沒有發生，取而代之出現的是分子間脫水反應，分別對應產生了8f、8g和8h；在氯仿為溶劑溫度達攝氏50度的環境中，鄰-丙炔苯基酮1h與[Ru]-Cl 可以進行催化劑量之環化反應，產生苯駢哌喃的產物14h。接著，利用具有α,β-不飽和酮的1k-n與[Ru]-Cl在甲醇的環境中反應，亦可透過不同於前面環化方式，分別獲得相對應具有苯并环庚酮這樣大環的釕金屬亞乙烯基錯化合物10k-m和 11n，這樣的分子內環化反應是透過加成於不飽和雙鍵中的β碳而產生的，上述的所有反應產物都利用光譜的方式鑑定得到，此外，4a 和10l 此兩結構更利用X-ray 繞射確認。

關鍵字

釕金屬 ； 烯炔 ； 吡咯醛 ； 碳碳耦合 ； 丙炔苯甲醛 ； 雙核雙亞乙烯基

並列摘要

Ch1:In our investigation on the chemical reactions of N-propargyl pyrroles 1a-c containing aldehyde, keto and ester group on the pyrrole ring with [Ru]-Cl ([Ru] = Cp(PPh3)2Ru), an aldehyde group in the pyrrole ring is found to play a crucial role to stimulate cyclization reaction. The reaction of 1a containing an aldehyde group with [Ru]-Cl in the presence of NH4PF6 yields the vinylidene complex 2a which further reacts with allyl amine to give the carbene complex 6a with a pyrrolizine group. However, if 1a is first reacted with allyl amine to yield the iminenyne 8a, then the reaction of 8a with [Ru]-Cl in the presence of NH4PF6 yields the ruthenium complex 9a containing cationic pyrrolopyrazinium group, fully characterized by X-ray diffraction analysis. These results can be adequately explained by two processes after the triple bond of the propargyl group is coordinated to the Ru metal center. Namely, competing formation of a vinylidene intermediate vs direct nucleophilic attack control the reaction pathway. Additionally deprotonation of 2a by R4NOH yields the neutral acetylide complex 3a. In the presence of NH4PF6, attempted alkylation of 3a resulted in the formation the Fischer-type amino-carbene complex 5a due the presence of NH3 serving as a nucleophile. Using KPF6, alkylations of 3a with ethyl- and benzyl-bromoacetates afforded the disubstituted vinylidene complexes 10a and 11a containing ester groups, which underwent deprotonation reactions to give the furyl complexes 12a and 13a, respectively. For 13a containing an O-benzyl group, a subsequent 1,3-migration of the benzyl group is observed to yield the product 14a with a lactone unit. Similar reactivity was not observed for the corresponding N-propargyl pyrroles 1b and 1c containing keto and ester groups on the pyrrole ring.
Ch2:A remarkable intermolecular dehydrative coupling reaction with formation of a C-C bond was found for the vinylidene complex 2a, yielding the dinuclear bisvinylidene complex 4a. Complex 2a containing 1-hydroxyindan moiety was first formed from the reaction of o-propynyl benzaldehyde 1a with [Ru]-Cl ([Ru] = Cp(PPh3)2Ru) by a cyclization process. For analogous aldehyde 1b containing an additional 1,3-dioxolane group on the aryl ring, similar intermolecular coupling yields the dinuclear bisvinylidene complex 4b. However, the fluoro group on the aryl ring in aldehyde 1c inhibits the coupling reaction, thus the reaction gives only the vinylidene complex 2c. For the reactions of [Ru]-Cl in MeOH with compounds 1f, 1g and 1h, each with a ketone functionality, cyclization gives the vinylidene complexes 2f, 2g and 2h, respectively. However, no similar intermolecular coupling was observed, instead, the intramolecular dehydration yields 8f, 8g and 8h, respectively. In CDCl3, catalytic cyclization is observed for the o-propynylphenyl ketone 1h with [Ru]-Cl at 50 °C giving the isochromene products 14h. Furthermore, treatment of the o-propynylaryl α,β-unsaturated ketones 1k-m and 1n with [Ru]-Cl in MeOH affords the corresponding vinylidene complexes 10k-m and 11n each with 1-benzosuberone moiety in the presence of NH4PF6. These intramolecular cyclization products are formed by the addition of Cβ onto the terminal carbon of the alkene moiety. All these reaction products are characterized by spectroscopic methods. In addition, structures of complexes 4a, and 10l are confirmed by single crystal X-ray diffraction analysis.

並列關鍵字

Ruthenium ； enyne ； pyrrolecarboxyaldehyde ； C-C couplin ； propynyl benzaldehyde ； dinuclear bisvinylidene

參考文獻

Ch1

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