由含炔基與醛或酮基之苯衍生物合成釕金屬亞乙烯基化合物之環化與分子間或分子內之脫水反應研究

Cyclization and Subsequent Intermolecular Dehydrative Coupling and Comparative Intramolecular Dehydration of Ruthenium Vinylidene Complexes from Aromatic Propynes Containing Carbonyl Functionalities

郭誠宸(Cheng-Chen Kuo)

指導教授 ： 林英智 ； 劉陵崗

國立臺灣大學/理學院/化學研究所/碩士(2014年)

https://doi.org/10.6342/NTU.2014.00143

摘要

利用釕金屬錯合物誘導鄰位具醛、酮或羥基取代的芳香末端炔環化反應已經被廣泛報導，此環化反應經由中間體釕金屬亞乙烯基，藉由亞乙烯基的Cα碳與具親核性的氧基生成碳－碳鍵得到釕金屬碳烯錯合物。於此，我們致力於探討釕金屬亞乙烯基的Cβ與具鄰位具羰基與丙炔基的芳香化合物之偶合反應。在利用釕金屬[Ru]-Cl ([Ru]=CpRu(PPh3)2) 誘導鄰丙炔基苯甲醛1a的反應中，環化反應由亞乙烯基的Cβ與羰基上的碳形成新的碳－碳鍵，得到具雙取代的五元環釕金屬亞乙烯基錯合物2a與分子間脫水偶合形成另一碳－碳鍵的產物雙金屬亞乙烯基錯合物3a。而我們也嘗試在鄰丙炔苯甲醛上做推電子基與拉電子基的修飾，在1b苯環上具1,3-二氧戊烷取代的反應中，得到釕金屬亞乙烯基錯合物2b’。將2b’溶於在二氯甲烷或是氯仿下可進行分子間脫水偶合得到雙金屬亞乙烯基錯合物3b’。然而在2-丙炔,4-氟苯甲醛中，因拉電子基的緣故，反應只有得到環化後的釕金屬亞乙烯基錯合物2c’。此外，我們也嘗試了一系列鄰位具酮基丙炔基的芳香化合物進行反應，在1d-f與1k-m與釕金屬[Ru]-Cl的反應中，也分別得到環化後的釕金屬亞乙烯基錯合物2d-f與2k-m’。不同的是2d、2k與2m’可以進一步進行分子內脫水反應,得到脫水後的釕金屬亞烯烯基錯合物5d、5k與5m。特別的是將5m於甲醇中加熱，未飽和碳碳雙鍵攻擊亞乙烯基的Cα生成新的碳－碳鍵並進行脫金屬反應，得到有機物產物芴8。當在酮基上修飾α,β未飽和碳碳雙鍵時，釕金屬亞乙烯基的Cβ與未飽和碳碳雙鍵進行分子內環化，得到具七元環的雙取代亞乙烯基錯合物。此外，將酮基上具苄基取代得有機物與催化量的[Ru]-Cl進行反應，可以得到isochrome衍生物9。.上述所有反應產物均藉由NMR與質譜分析鑑定。其中釕金屬亞乙烯基錯合物3a、5d、2e與6h的結構更進一步由X-ray單晶繞射分析技術確定。

關鍵字

釕金屬 ； 亞乙烯基 ； 環化 ； 脫水 ； 分子間偶合 ； 催化

並列摘要

Cyclization of terminal aromatic alkynes containing ortho-substituted aldehyde, ketone or hydroxyl functionality on the aryl ring induced by ruthenium complex is known to proceed via formation of vinylidene intermediate followed by an oxygen attack at Cα to give carbene complexes. However, our development on the coupling of the carbonyl functionality with Cβ of the vinylidene moiety yielded different final products. In the [Ru]-Cl induced ([Ru]=CpRu(PPh3)2) reaction of o-propynyl benzaldehyde 1a the vinylidene complex 2a containing a 1-hydroxyindan moiety, bonded at Cβ and carbonyl carbon, and the dinuclear bisvinylidene complex 3a are isolated. No intramolecular dehydration is possible for 2a. Therefore, the dinuclear complex 3a is produced by a new process of intermolecular dehydrative coupling of 2a yielding a new C-C bond. For aldehyde 1b containing a 1,3-dioxolane group on the aryl ring, the cyclization reaction takes place at Cβ first giving the intramolecular cyclized vinylidene complex 2b’, which similarly undergoes intermolecular coupling to yield the dinuclear bisvinylidene complex 3b’. However, in the reaction of 1c, containing an electron-withdrawing fluoro group in the para-position of aldehyde, with [Ru]-Cl, no further intermolecular coupling happens, instead, only the disubstituted vinylidene complex 2c’ is obtained by intramolecular attack of Cβ onto carbonyl group. Additionally, in the reaction of o-propynylphenyl ketone derivatives 1d-f and 1k-m, the cyclized ruthenium vinylidene complexes 2d-f and 2k-m’, respectively, are also obtained and further intramolecular dehydration takes place in the case of 2d, 2k and 2m’, affording complexes 5d, 5k and 5m. Furthermore, treatment of the o-propynylphenyl α,β-unsaturated ketone 1g-i and 1j with [Ru]-Cl in the presence of NH4PF6 in MeOH afforded the vinylidene complex 6g-i and 7j with 1-benzosuberone moiety. This intramolecular cyclization product was produced by the nucleophilic addition of Cβ onto the alkene part. Interestingly, when heating the 5k in MeOH at 50 °C, the sequential cyclization is proceeded via nucleophilic attack of the unsaturated alkenes onto the electrophilic Cα of vinylidene moiety, giving the demetallation product fluorene 8. Additionally, heating the o-propynylphenyl ketone 1m in CDCl3 with [Ru]-Cl at 50 °C gives the catalytic products 1-benzylidene-3-methyl-1H-isochromene 9. All these reaction products are characterized by spectroscopic methods. In addition, structures of complexes 3a, 5d, 2e and 6h are confirmed by X-ray diffraction analysis.

並列關鍵字

Ruthenium ； vinylidene ； cyclization ； dehydration ； intermolecular coupling ； catalysis

參考文獻

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