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Investigations On Vinyl Diazonium Ions As Electrophiles For Nucleophilic Addition And Use Towards The Total Synthesis Of Anadensin
Rose, Benjamin J.
Rose, Benjamin J.
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Abstract
Vinyl diazonium ions can lose molecular nitrogen to give vinyl cations or can act as electrophiles in diazoretentive conjugate addition reactions. The research described in this dissertation investigates both of these reactivities. The scope of the diazoretentive conjugate addition of vinyl diazonium ions, was assessed with respect to different nucleophilic partners. Using Mayr’s scale for nucleophilicity, we determined that likely nucleophiles for this reaction were; Boron-ate complexes, enamides, and allyl stannanes. While investigating the ability of these nucleophiles to add to vinyl diazonium salts, I observed that allyl stannanes were competent reaction partners giving -allyl--diazocarbonyl products in high yields. Boron-ate complexes and enamides did not give the desired addition products.
Prior work in our group has shown that cyclic vinyl cations, formed from vinyl diazonium ions, undergo an annulative ring expansion followed by a remote C-H insertion to form cyclopentanones fused to medium-sized rings. It was proposed that this reactivity could be taken advantage of to access the 5,8,5-tricyclic core of the natural product anadensin. My efforts towards the total synthesis of anadensin, including the synthesis of one of the important intermediates, a 5,7-fused bicyclic structure resembling the daucane class of natural products is described herein. Applications toward the synthesis of duacane natural products, felikiol and daucon are also described.
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2025
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Rose_uvm_0243D_11956.pdf
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