Visible-Light-Induced Highly Site-Selective Direct C-H Phosphorylation of Pyrrolo[2,3-d]pyrimidine Derivatives with H-Phosphine Oxides.

An efficient and highly regioselective C6-phosphorylation protocol for pyrrolo[2,3-d]pyrimidine (7-DAP) derivatives with various H-phosphine oxides induced by visible light at room temperature is described for the first time. This protocol has been successfully achieved by the combination of Na2-eosin Y as a photocatalyst and LPO as an oxidant under transition metal- and additive-free conditions. The broad substrate scope, good functional group tolerance, excellent regioselectivity, and air tolerant conditions make this process favorable for the functional modification of pyrrolo[2,3-d]pyrimidine scaffold and enrich the phosphorylated 7-DAP compounds for further biological evaluation.

Pd-Catalyzed solvent-controlled site-selective arene C-H monoacyloxylation of pyrrolo[2,3-d]pyrimidine derivatives.

An efficient and highly regioselective Pd-catalyzed direct arene C(sp2)-H acyloxylation of pyrrolo[2,3-d]pyrimidine derivatives is reported. The key strategy involves the utilization of the unique reactivity of pyrrolo[2,3-d]pyrimidine and the employment of pyrrolo[2,3-d]pyrimidine as the directing group. A variety of monoacyloxylated pyrrolo[2,3-d]pyrimidine derivatives can be achieved by switching the solvents under mild conditions, and they can be further modified and exhibit various biological activities.