Convenient, practical and economical phosphorylation of thiols has been achieved via halogen- and metal-free K2CO3-promoted aerobic oxidative cross-coupling of trialkyl phosphites, dimethyl phenylphosphonite, or methyl diphenylphosphinite with thiophenols using air as the oxidant at room temperature. This transformation provides a straightforward route to the construction of phosphorus–sulfur bonds with wide functional group compatibility, which affords phosphorothioates in up to 94% yield.

•The cross dehydrogenative coupling reaction of thiophenols with acetonitrile has been achieved.•The reactions afford sulfenylated acetonitriles in the presence of Cs2CO3 and air.•The protocol is halogen-, metal-, and strong oxidant-free.A novel protocol for the construction of carbon–sulfur bonds has been achieved via halogen-free Cs2CO3-promoted cross dehydrogenative coupling (CDC) of thiophenols with acetonitrile. This transformation provides a straightforward route to the synthesis of sulfenylated acetonitriles in up to 80% yield.Download high-res image (42KB)Download full-size image

A convenient and efficient α-sulfenylation of carbonyl compounds has been achieved via the halogen-free Cs2CO3-promoted cross-dehydrogenative coupling (CDC) of thiophenols with active methylene compounds using air as the oxidant under mild conditions. This transformation provides a straightforward route to the construction of carbon–sulfur bonds with wide functional group compatibility, which produces α-sulfenylated carbonyl compounds in up to 95% yield.

•The oxidation of P(III) compounds with Selectfluor smoothly affords P(V) compounds in high yields.•The reactions give tertiary phosphine oxides, phosphinates, and phosphonates at room temperature in minutes.•The oxidation conditions are mild, user-friendly, and safe.A novel and efficient oxidation of phosphorus(III) compounds with Selectfluor is described. The reactions smoothly led to the formation of tertiary phosphine oxides, phosphinates, and phosphonates in up to 99% yield under mild conditions in minutes.

An efficient P-arylation of secondary phosphine oxides has been achieved through the ligand-free copper-catalyzed addition of H–P(O) bonds to in situ generated arynes at room temperature. This transformation provides a straightforward route to the formation of the aryl–P bond with wide functional group compatibility, which produces arylphosphine oxides in up to 99% yield.

The novel P-arylation of dialkyl phosphites and secondary phosphine oxides with arynes has been achieved. The reactions produce dialkyl arylphosphonates in 71–99% yield and tertiary phosphine oxides in 68–92% yield under mild conditions.

A novel and efficient electrophilic fluorination of secondary phosphine oxides with Selectfluor has been achieved. This transformation provides direct access to phosphoric fluorides in up to 92% yield under mild conditions. In addition, P–O bond construction via a one-pot coupling process of secondary phosphine oxides with water or alcohols in the presence of Selectfluor leads to the formation of phosphinic acids or phosphinates in up to 96% yield.

The insertion of arynes into the O–H bond of aliphatic carboxylic acids promoted by sodium carboxylates is described. The reactions led to the formation of aryl carboxylates in good yields with good chemoselectivities under mild conditions.

The efficient α-monoarylation and tandem arylation–insertion of malonates with arynes, generated by fluoride-induced elimination of Kobayashi’s silylaryl triflates, are described. The reactions led to the formation of α-arylmalonates in up to 88% yield with high chemoselectivities and diarylmethane derivatives in good yields under mild conditions.