Lantibiotics such as nisin are active against most Gram-positive bacteria and constitute an important class of antibacterial agents. These ribosomally synthesized peptides contain either one or both of the unusual amino acids meso-lanthionine (m-Lan) or β-methyllanthionine (β-MeLan). Nucleophilic ring opening of sulfamidates allows facile preparation of stereochemically pure derivatives of m-Lan and β-MeLan with orthogonal protection for solid phase synthesis of lantibiotic analogues.