Copper-Catalyzed Oxidative sp-Carbon Radical Cross-Coupling with Trialkylphosphites Leading to α-Phosphonyl 1,3-Dicarbonyl Compounds.

A copper-catalyzed radical C-H/P(OR) cross-coupling reaction for the formation of C-P bonds is described. A range of 1,3-dicarbonyl compounds and trialkylphosphites were coupled in this fashion to give the corresponding products in moderate to good yields. This protocol provides direct access to α-phosphonyl 1,3-dicarbonyl compounds.

Copper-catalyzed TEMPO oxidative cleavage of 1,3-diketones and β-keto esters for the synthesis of 1,2-diketones and α-keto esters.

A copper-catalyzed efficient and practical method has been developed for the synthesis of 1,2-diketones and α-keto esters. TEMPO was used as a radical initiator and scavenger, oxidizing the cleavage of α-methylene of 1,3-diketones and β-keto esters to form 1,2-diketones and α-keto esters. This method provided a general way for the formation of 1,2-dicarbonyl compounds.

Air Oxidative Radical Oxysulfurization of Alkynes Leading to α-Thioaldehydes.

Air oxidative radical oxysulfurization of alkynes initiated by 0.5 mol % tert-butyl hydroperoxide with arylthiols is described. The reaction proceeded at room temperature in the presence of 5% mol water to afford selective α-thioaldehydes.

Manganese(III)-mediated alkenyl C(sp2)-P bond formation from the reaction of β-nitrostyrenes with dialkyl phosphites.

Mn(OAc)3-mediated tandem phosphonyl radical addition to β-nitrostyrenes followed by denitration to form (E)-2-alkenyl phosphonates in good yield is described.

Air oxidative radical hydroxysulfurization of styrenes leading to β-hydroxysulfides.

Air oxidative radical hydroxysulfurization of styrenes initiated by 0.5 mol % of tert-butyl hydroperoxide with arylthiols is described, and a new type of difunctionalization of alkenes was achieved.

Direct radical acetoxyphosphorylation of styrenes mediated by manganese(III).

Direct radical acetoxyphosphorylation of styrenes mediated by Mn(OAc)3 with diphenylphosphine oxide and dialkyl phosphites was described, and a new type of difunctionalization of alkenes was achieved.