A silver-catalyzed dehydrogenative cross-coupling reaction of substituted furans, thiophene, thioazole, and pyrrole 1a-e with dialkyl phosphites 2 was first developed to afford corresponding phosphonated products 3a-h with up to 89% yield and good regioselectivities. Moreover, an unprecedented coupling of various substituted pyridines 1f-k with dialkyl phosphites 2 using AgNO(3) as a catalyst and K(2)S(2)O(8) as an oxidant, followed by reduction with Na(2)S(2)O(3), was also realized to furnish desired pyridine phosphonates 3i-q in satisfactory yields with good regioselectivities.

A domino oxidation-acyloxylation reaction of 2-arylpyridines with aldehydes or methylarenes under the catalysis of Cu(OAc) 2 has been developed. The strategy via C-H bond functionalization has the advantages of good functional-group tolerance, high ortho regioselectivity and no need of any ligand or additive.

Carboxylic acids, generated in situ by oxidation of aldehydes or methyl arenes, react with substrates (I) and (IX) to afford the desired acyloxylated products with high ortho selectivity.

The Pechmann dehydration reaction of cyclohexanone derivatives with phenols yields coumarin‐fused cyclohexadiene intermediates.

An efficient method to prepare various heteroaromatic phosphonates is reported.