Facile and Efficient Synthesis of Lactols by a Domino Reaction of 2,3‐Epoxy Alcohols with a Hypervalent Iodine(III) Reagent and Its Application to the Synthesis of Lactones and the Asymmetric Synthesis of (+)‐Tanikolide

The domino reaction of 2,3‐epoxy‐1‐alcohol derivatives, namely tetrasubstituted 2,3‐epoxy‐1‐alcohols and 2‐ or 3‐alkyl trisubstituted 2,3‐epoxy‐1‐alcohols, with PhI(OCOCF 3 ) 2 in the presence of H 2 O is described in detail. In this reaction, several types of lactol derivatives can be directly obtained from the 2,3‐epoxy‐1‐alcohol derivatives in a single operation. The obtained lactols were successively converted into the corresponding lactones. This reaction is applicable to the construction of optically active lactone compounds. The asymmetric total synthesis of (+)‐tanikolide, an antifungal marine natural product, has been effectively achieved by using this reaction.