Divergence of carbonyl ylide reactions as a function of diazocarbonyl compound and aldehyde substituent: dioxolanes, dioxolenes, and epoxides.
The products from dirhodium(II) acetate-catalyzed reactions between diazocarbonyl compounds and a series of benzaldehydes demonstrate the extent of competition between intramolecular and intermolecular trapping of carbonyl ylide intermediates and the electronic effects that govern these transformations. With dimethyl diazomalonate, competition exists between dioxolane and epoxide formation so that with p-anisaldehyde only epoxide formation is observed and with p-nitrobenzaldehyde only 1,3-dioxolane products are formed. With methyl diazoacetoacetate, intramolecular trapping of the intermediate carbonyl ylide results in the sole production of dioxolenes. However, the vinyldiazoacetate analogue of methyl diazoacetoacetate, as its tert-butyldimethlsilyloxy derivative, only produces epoxides in its reactions with substituted benzaldehydes.
Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland, 20742, USA.
Albert E
AE
Russell
Jonathan
J
Brekan
Luisa
L
Gronenberg
Michael P
MP
Doyle
D001547:Benzaldehydes / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D003979:Diazonium Compounds / Q000737:chemistry*; D004852:Epoxy Compounds / Q000737:chemistry*; D007202:Indicators and Reagents; D008958:Models, Molecular; D015394:Molecular Structure; D012238:Rhodium / Q000737:chemistry*
D001547:Benzaldehydes; D003979:Diazonium Compounds; D004852:Epoxy Compounds; D007202:Indicators and Reagents; D012238:Rhodium