Convenient tool for the synthesis of β-thiol containing oligopeptides suitable for chemical conjugation or for the formation of organic monolayers on metal substrates. The cleavage from the resin with TFA/water/triisopropylsilane (94:4:2, v/v/v) yields C-terminal thiols. Linkage of these thiols e.g. to maleimides can be performed under very mild conditions.