Reactivities and selectivities in macrocyclic addition reactions with diazoacetates using copper(I) and rhodium(II) catalysts

Reactions of diazoacetates linked through three ethylene glycol units to allyl, methallyl, propargyl, or furfuryl, catalyzed by copper(I) and rhodium(II) compounds, are investigated for chemoselectivity, diastereoselectivity, and enantioselectivity. The most reactive catalysts show the highest preference for addition over carbon–hydrogen insertion. Addition is favored in the order: prapargyl>furfuyl>methallyl, allyl.