Synthesis of (−)-Sordarin

The first total synthesis of (−)-sordarin (1) was accomplished exploiting the following key reactions: (i) Ag(I)-catalyzed oxidative radical cyclization of a cyclopropanol derivative leading to a bicyclo[5.3.0]decan-3-one skeleton; (ii) Pd(0)-catalyzed intramolecular allylation reaction resulting in the entire strained bicyclo[2.2.1]heptan-2-one framework of sordaricin (2); (iii) selective dihydroxylation of terminal alkenes by the combined use of OsO4 and PhB(OH)2; and (iv) β(1,2-cis)-selective glycosidation via a 1,3-anchimeric assistance from a 4-methoxybenzoyl group.