Remote stereocontrol in [3,3]-sigmatropic rearrangements: application to the total synthesis of the immunosuppressant mycestericin G.

The Ireland-Claisen [3,3]-sigmatropic rearrangement has been used to access biologically important β,β'-dihydroxy α-amino acids. The rearrangement reported is highly stereoselective and offers excellent levels of remote stereocontrol. This strategy has been used to synthesize the natural immunosuppressant mycestericin G and ent-mycestericin G, allowing for a revision of absolute configuration of this natural product.