Total Synthesis of (+)‐Tanikolide by a Traceless Stereoinduction Method Using Rhodium(II)‐Catalyzed Oxonium Ylide Formation—[2,3]‐Sigmatropic Rearrangement and NHC‐Catalyzed Ring‐Expansion Lactonization.

The total synthesis of (+)-tanikolide was accomplished by a traceless stereoinduction method using the key steps of a Rh(II)-catalyzed oxonium ylide formation–[2,3]-sigmatropic rearrangement and an N-heterocyclic carbene-catalyzed ring-expansion lactonization of tetrahydrofurfural. This synthetic route is applicable to the divergent synthesis of tanikolide analogues.