Enantioselective Synthesis of Spiroacetals via Silver(I)-Promoted Alkylation of Hemiacetals: Total Synthesis of Cephalosporolides E and F

A silver(I)-promoted intramolecular hemiacetal alkylation has been developed that converts readily available keto-chlorodiols into functionalized spiroacetals containing 5,5-, 5,6-, and 5,7-membered ring systems. The efficiency of this process is demonstrated in a concise total synthesis of the fungal metabolites cephalosporolides E and F.