Add time:07/13/2019 Source:sciencedirect.com
The SP-isomer of 5′-OH-N4-benzoyl-2′-deoxycytidine-3′-O-(2-thio-4,4-pentamethylene-1,3,2-oxathiaphospholane) undergoes DBU-promoted intramolecular cyclization providing as a sole product SP-deoxycytidine cyclic 3′,5′-O,O-phosphorothioate. Unexpectedly, the RP-counterpart yields a mixture of products consisting of RP-deoxycytidine cyclic 3′,5′-O,O-phosphorothioate and macrocyclic oligo(deoxycytidine phosphorothioate)s. The results of molecular modeling indicate that the dychotomy observed for the RP substrate may result from remarkably higher energy of the corresponding transition states, caused by the presence of bulky ‘spiro’ pentamethylene substituent at the position C4 in the oxathiaphospholane ring.
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