Two types of reactivities of thiophosphates have been demonstrated: one being nucleophilic displacement by the P-S moiety of nucleoside phosphorothioates and the other, phosphorylation via P-S cleavage as the driving force. We have designed a system where both displacement on carbon and P-S cleavage are possible. Adenosine derivatives have been synthesized with 5'-deoxy-5'-chloro and 5'-O-tosyl substitutions as leaving groups utilizing the 3'-O-phosphorothioate as the biphilic center. The main products of cyclization were 5'-O-tosyl and 5'-chloroadenosine 2':3'-cyclic phosphate. Formation of 3':5'-S-phosphorothioate was slow even using an excellent leaving group. This is possibly due to hydrogen bonding between the 2'-OH and the neighboring P-O.--KOH hydrolysis of the cyclic phosphorothioate yielded 2'(3') phosphorothioates in a 1:1 ratio. The 2' and 3' isomers were separated and used to study the relative rates of cyclization. The cyclization via P-S cleavage of 2'(3')-O-phosphorothioates showed that the 2' isomer was more reactive. This is the first report of superior reactivity of the 3'-OH of a ribonucleoside.