Synthesis, Transformations, And Comparative Studies of Porphyryl Acrylic Acids and Their Homologues

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• 作者：Natalia N. Sergeeva^† ; ; Mohd B. Bakar^† ; ; Mathias O. Senge*^† ; ^‡ ;
• 刊名：Journal of Organic Chemistry
• 出版年：2009
• 出版时间：February 20, 2009
• 年：2009
• 卷：74
• 期：4
• 页码：1488-1497
• 全文大小：367K
• 年卷期：v.74,no.4(February 20, 2009)
• ISSN：1520-6904

文摘

The reactivity of porphyryl acrylates and their homologues was studied systematically and to establish their potential as building blocks for the synthesis of novel tetrapyrroles. A new synthetic approach for multifunctional porphyrins was developed using α,β-unsaturated acyl porphyrins as versatile building blocks with yields of 44−95%. The reaction of acyl chlorides generated in situ with ethyl diazoacetate in the presence of PPh₃ led to the corresponding phosphazine, which was quickly self-transformed into a novel porphyrin β-keto ester system in up to 78% yield. Comparative studies of the next homologue of acrylic porphyrins, i.e., those bearing an additional CH₂ group next to the double bond of the α,β-unsaturated fragment, showed that these can undergo rearrangement reactions via vinylketenes to yield both regioisomers. Depending on the reaction conditions, this method gives regioselectively access to either a rearrangement product or the product of esterification reactions in yields of 81% or 57%, respectively. Enyne metathesis of novel propargyl esters with allyl porphyrins provided an easy access to 1,3-disubstituted butadienes in up to 76% yield.