Regioselective and Enantiospecific Synthesis of Dioxepines by (Cyclopentadienyl) ruthenium-Catalyzed Condensations of Diazocarbonyls and Oxetanes

1,4-Dioxepines result from the decomposition of alpha-diazo-beta-keto esters in the presence of oxetanes using the catalytic combination of the (cyclopentadienyl) ruthenium complex [CpRu(CH3CN)(3)][BArF] and 1,10-phenanthroline. The regioselective [4+3] insertions follow an S(N)1-like mechanism and occur yet enantiospecifically (es 74%). The retention of configuration was ascertained by vibrational circular dichroism (VCD) and solid state analyses. Furans, products of [4+1] insertions, are only observed as traces in the above protocol. To promote their formation under CpRu catalysis, it is necessary to use a two-step process with gamma-halogenated alcohols as substrates.