The α2β2 complex of tryptophan synthase from Escherichia coli catalyzes β-replacement reactions of l-serine and its derivatives (eg., β-chloro-l-alanine and O-methyl-Dl-serine) with various alkanethiols. The products from thiobenzyl alcohol and ethanethiol were isolated to demonstrate the enzymatic synthesis of the corresponding S-substituted l-cysteines. Reactivities of various S-substituent donors were examined, and thiols such as thiobenzyl ...