The technique of native chemical ligation enables the total chemical synthe
sis of proteins. This method is limited, however, by an absolute requiremen
t for a cysteine residue at the ligation juncture. Here, this restriction i
s overcome with a new chemical ligation method in which a phosphinobenzenet
hiol is used to link a thioester and azide. The product is an amide with no
residual atoms.