Three- to six-carbon ring-enlargement reaction of cyclic ortho esters bearing a diazocarbonyl side chain. Use of the intramolecular formation of tricyclooxonium ylides

Two types of bicyclic ortho esters 14 and 18, which are tethered to a diazocarbonyl group by polymethylene linkages--(CH2)n--of different lengths (n = 1-3 for 14 and 1-4 for 18), were prepared and catalytically decomposed by treatment with Rh2(OAc)4 either in the presence or absence of a protic nucleophile (MeOH, PhOH, AcOH) to give ring-enlargement product lactones 25 and 30 of different sizes. With 14, the enlargement took place when n = 1 or 2, but not when n = 3. With 18, in which the diazo carbon is substituted with a methoxycarbonyl group, the length of the chain can be extended further to n = 4 to obtain ring-enlargement products or their derivatives. All of these reactions could be explained in terms of the intermediacy of tricyclooxonium ylides 22 and 28. The ylides form an equilibrium with the corresponding ring-opened zwitterions 22' and 28', respectively, which, after protonation by a protic nucleophile, undergo mainly ring-enlargement to form medium-sized or large oxalactones rather than 1,2-rearrangement.