Synthesis of Functionalized Diazoacetoacetates via Mukaiyama-type Condensations

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dc.contributor.advisorDoyle, Michael Pen_US
dc.contributor.authorLiu, Yuen_US
dc.contributor.departmentChemistryen_US
dc.contributor.publisherDigital Repository at the University of Marylanden_US
dc.contributor.publisherUniversity of Maryland (College Park, Md.)en_US
dc.date.accessioned2012-07-10T05:30:38Z
dc.date.available2012-07-10T05:30:38Z
dc.date.issued2011en_US
dc.description.abstractMukaiyama-type condensation reactions of 3-<italic>tert</italic>-butyldimethylsiloxy-2-diazo-3-butenoate and different electrophiles are effective methods for the synthesis of highly substituted diazoacetoacetates. With 0.5-3 mol% of Zn(OTf)<sub>2</sub> as Lewis acid catalyst, Mukaiyama-Michael reactions of vinyldiazoacetates and &alpha,&beta-unsaturated ketones proceed at ambient temperature to afford functionalized diazoacetoacetates in good yields. By carefully choosing the reaction conditions, both Mukaiyama-Michael adducts in either silyl enol ether form or in ketone form can be synthesized. Addition products obtained from these Mukaiyama-Michael reactions are investigated in dirhodium(II) catalyst induced dinitrogen extrusion reactions. Enedione-diazoester derived from Mukaiyama-Michael reaction of 3-<italic>tert</italic>-butyldimethylsiloxy-2-diazo-3-butenoate and 4-methoxy-3-bute-2-one can be converted to resorcinol derivatives under base catalysis. This novel transformation was investigated and developed into a synthetic methodology for the preparation of poly-substituted resorcinol compounds. Orthoesters also react with 3-<italic>tert</italic>-butyldimethylsiloxy-2-diazo-3-butenoate in the presence of Lewis acid catalysts. Diazoacetoacetates that contain acetal functionality can be assembled by these reactions. Rhodium(II) acetate promoted dinitrogen extrusion reactions of these adducts can give &beta-alkoxycyclbutanone products, which are useful synthons in organic synthesis.en_US
dc.identifier.urihttp://hdl.handle.net/1903/12771
dc.subject.pqcontrolledChemistryen_US
dc.subject.pquncontrolled3-alkoxycyclobutanoneen_US
dc.subject.pquncontrolleddiazoacetoacetatesen_US
dc.subject.pquncontrolleddirhodium catalysten_US
dc.subject.pquncontrolledMukaiyama-Michaelen_US
dc.subject.pquncontrolledresorcinolen_US
dc.titleSynthesis of Functionalized Diazoacetoacetates via Mukaiyama-type Condensationsen_US
dc.typeDissertationen_US
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