Alkaline Earth Metals in Synthesis

When was the last time you used a calcium, magnesium, strontium or barium catalyst in organic synthesis?

I suspect many have never used one at all.  Well a recent article (Angew Chem Int Ed, 2009, 48, 5790) by Uli Kazmaier reviews recent work in the area.  Owing to their low cost and abundance as well as low toxicity, industry should be looking at using them more often in reactions.  The article discusses recent work on Michael, Aldol and Mannich reactions using alkaline earth catalysts, especially asymmetric versions, when high d.e and ee can be obtained.

In the Mannich reaction,  for example, syn/anti selectivity can be changed simply by changing from, say,  a magnesium to a barium catalyst.