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|Title: ||Synthesis of Functionalized Diazoacetoacetates via Mukaiyama-type Condensations|
|Authors: ||Liu, Yu|
|Advisors: ||Doyle, Michael P|
|Sponsors: ||Digital Repository at the University of Maryland|
University of Maryland (College Park, Md.)
3-alkoxycyclobutanone, diazoacetoacetates, dirhodium catalyst, Mukaiyama-Michael, resorcinol
|Issue Date: ||2011|
|Abstract: ||Mukaiyama-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.|
|Appears in Collections:||UMD Theses and Dissertations|
Chemistry & Biochemistry Theses and Dissertations
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