K2S2O8 promoted C–H direct thiocyanation of pyrrolo[2,3-d]pyrimidine derivatives with ammonium thiocyanate

K2S2O8-promoted highly efficient and site-selective direct C–H thiocyanation of pyrrolo[2,3-d] pyrimidine (7-DAP) derivatives with NH4SCN at room temperature was developed. This protocol exhibits broad substrate scope, good functional group tolerance and operational simplicity. This methodology is favourable for the functional modification of pyrrolo[2,3-d] pyrimidines scaffold and enriches the library of thiocyanated 7-DAP compounds for the further biological evaluation. Importantly, the thiocyanated pyrrolo[2,3-d]pyrimidines are readily converted to other potential pharmaceutically important sulfur-containing motifs. [Display omitted] •The site-selective direct C–H thiocyanation of pyrrolo[2,3-d]pyrimidine and other heteroarenes was realized.•The free radical thiocyanation is involved.•K2S2O8 plays a vital role for this unique reactivity.•A wide range of functional groups are tolerated in this protocol.