The acyloin natural products are a family of bioactive compounds isolated from fungi and myxobacteria. The total synthesis of 7 members of the acyloin family was achieved via a HWE reaction followed by Mukaiyama–Isayama hydration, using novel Co(II) and Co(III) Schiff base SALPN complexes as catalysts for the key enone hydration step. Furthermore, we have shown that a mild acyloin rearrangement is possible under Mukaiyama hydration conditions, which was crucial in the success of this approach.