We report various unusual amino acid derivatives containing heterocycles and heteroatoms (S, O, N) via diethyl acetadimalonate as a glycine equivalent and carried out further chemical transformations to modify these unusual amino acid derivatives. Sulfur‐containing halo and alkene derivatives are prepared, and these substrates are further modified by Suzuki‐Miyaura cross‐coupling reaction, cross metathesis sequence and selective formation of sulfoxide and sulfone derivatives. We also report oxazole‐containing amino acid derivative by using TosMIC.