The fragmentation of primary alkoxyl radicals has been scarcely used in synthesis since other competingprocesses (such as oxidation or hydrogen abstraction) usually predominate. However, when serinederivatives were used as substrates, the scission took place in excellent yields. Tandem scission-allylation,-alkylation, or -arylation reactions were subsequently developed. This one-pot methodology was appliedto the synthesis of unnatural amino acids, which are useful synthetic blocks or amino acid surrogates inpeptidomimetics.