The total synthesis of sphingofungin F through the Overman rearrangement of an unsaturated ester, which is known to be an unsuitable substrate under standard conditions due to the competitive aza-Michael reaction, is described. The developed conditions enabled the ester to be compatible with the original Overman rearrangement, providing quick access to α,α-disubstituted amino acids by minimizing extra protecting group manipulations and redox reactions.