P. E. O'bannon, W. Dailey
Jun 23, 1989
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0
Influential Citations
33
Citations
Journal
Journal of Organic Chemistry
Abstract
Ethyl 1-nitrocyclopropanecarboxylates are formed in the reaction between alkenes and ethyl nitrodiazoacetate using a catalytic amount of rhodium(II) acetate. Ethyl oxo(hydroxy(alkyl-2-propenyl)amino) acetates are obtained as side products. These result from an ene reaction between the alkene and an intermediate acyl nitroso compound. Relative reactivities and stereoselectivities for catalytic rhodium(II) acetate reactions of ethyl nitrodiazoacetate with 12 alkenes to yield cyclopropanes and ene products are reported. Electron-rich, sterically undemending alkenes are the most reactive and give the best yields of cyclopropanes. Less reactive, crowded alkenes give poor yields of cyclopropanes and enhanced-yields of ene products. A comparison with the relevant data for ethyl diazoacetate reveals that the reaction with ethyl nitrodiazoacetate is more sensitive to the electronic and steric nature of the reactant alkene. Doyle's model for catalytic cyclopropanation with rhodium(II) acetate is invoked to explain these data.