釕金屬錯合物與芳香族分子進行分子內環化反應
之研究:碳-碳鍵與碳-氧鍵的斷裂與形成

陳易新

doi:10.6342/NTU.2013.01208

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釕金屬錯合物與芳香族分子進行分子內環化反應之研究:碳-碳鍵與碳-氧鍵的斷裂與形成

Study on the Intramolecular Cyclization Reactions of Aromatic Compounds on Ruthenium Metal Center

陳易新 , Masters　　Advisor：林英智　　

英文 DOI： 10.6342/NTU.2013.01208

釕金屬；擴環反應；含氧五環；含氧七環；環化反應； Ruthenium ； acetylide ； vinylidene ； allenylidene ； phosphonium acetylide ； cyclization

Abstract │ Reference (45) │ Altmetrics

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The reaction of [Ru]Cl ([Ru] = Cp(PPh3)2Ru) with 1,6-enyne compounds, in which the triple bond of enyne is associated with a propargylic alcohol and the olefinic group of enyne having various substituted methyl groups is modified by changing the olefinic group to contain other functional groups, exhibits an intramolecular cyclization involving C-O bond formation and C-C bond formation. When the olefinic group is converted to give the epoxide with no substituted methyl group, the reactions of the substrate with [Ru]Cl in the presence of KF in MeOH at 50oC for one day afford the acetylide complex. This reaction takes place at the propargylic alcohol first giving the allenylidene complex as an intermediate, then MeOH attacks Cγ as a nucleophilic group via a C-O bond information to form the acetylide complex as a final product. Interestingly, by changing KF into KPF6 under the same condition, the acetylide complex continues to proceed an intramolecular cyclization at Cβ to open the epoxide group to yield the disubstituted vinylidene complex. This C-C bond formation occurs at Cβ, possibly assisted by the presence of KPF6, to form the disubstituted vinylidene complex. 
    The olefinic part of enyne substrate is also transformed to a hydroxy group as a nucleophile and a bromide group as a good leaving group. Reactions of these compounds with [Ru]Cl in the presence of KF in MeOH proceed tandem cyclization to form tricyclic complexes. The first step of the reaction involves dehydration of the propargylic group leading to the allenylidene complex. Then an intramolecular nucleophilic addition of the hydroxyl group to Cγ of the allenylidene ligand results in the acetylide complex as an intermediate, which is only transient possibly due to the presence of a near-by electrophilic group. Thus the second cyclization via a C-C bond formation cleaves the C-Br bond to form the tricycle ruthenium complex. This reaction proceeds by a cyclization reaction involving a propargylic alcohol, a nucleophilic group and an electronphilic group to form the vinylidene ligand with a tricyclic ring on the metal. The structures of the newly formed products are supported by their 1H, 31P and 13C NMR spectra. In order to gain further information to support the structure of these complexes, 2-D NMR spectra such as 1H,1H-COSY, 1H,13C-HSQC, 1H,13C-HMBC are also employed. These data indirectly corroborate the tandem cyclizations at Cβ and Cγ of the allenylidene ligand forming tricyclic complexes.

Reference ( 45 ) 〈TOP〉

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