Simple organocatalysts in multi-step reactions: An efficient one-pot Morita-Baylis-Hillman-type α-hydroxymethylation of vinyl ketones followed by the convenient, temperature-controlled one-pot etherification using alcohols

1,4-Diazabicyclo[2.2.2]octane (DABCO) was utilized as versatile catalyst in a one-pot synthesis: First, for the preparation of alcoholic formaldehyde solutions from para-formaldehyde catalysed by using low loadings of inexpensive DABCO. Second, for the fast α-hydroxymethylation of alkylic and aromatic vinyl ketones in high yields. In a third step, the same catalyst can be used for an optional, temperature controlled in situ etherification of the Morita-Baylis-Hillman product with various alcohols on a multi-gram scale in moderate to good overall yields and high purities. Furthermore, an application of the ether in the enantioselective synthesis of a common building block for total synthesis is shown, thus providing a gram-scale access from inexpensive bulk chemicals.