Palladium-Catalyzed Enantioselective Arylation of Aryl Sulfenate Anions: A Combined Experimental and Computational Study.

A novel approach to produce chiral diaryl sulfoxides from aryl benzyl sulfoxides and aryl bromides via an enantioselective arylation of aryl sulfenate anions is reported. A (JosiPhos)Pd-based catalyst successfully promotes the asymmetric arylation reaction with good functional group compatibility. A wide range of enantioenriched diaryl, aryl heteroaryl, and even diheteroaryl sulfoxides were generated.

Palladium-catalyzed α-arylation of benzylic phosphonates.

A new synthetic route to access diarylmethyl phosphonates is presented. The transformation enables the introduction of aromatic groups on benzylic phosphonates via a deprotonative cross-coupling process (DCCP). The Pd(OAc)2/CataCXium A-based catalyst afforded a reaction between benzyl diisopropyl phosphonate derivatives and aryl bromides in good to excellent isolated yields (64-92%).

Palladium-catalyzed α-arylation of benzylic phosphine oxides.

A novel approach to prepare diarylmethyl phosphine oxides from benzyl phosphine oxides via deprotonative cross-coupling processes (DCCP) is reported. The optimization of the reaction was guided by High-Throughput Experimentation (HTE) techniques. The Pd(OAc)2/Xantphos-based catalyst enabled the reaction between benzyl diphenyl or dicyclohexyl phosphine oxide derivatives and aryl bromides in good to excellent yields (51-91%).

Diaryl sulfoxides from aryl benzyl sulfoxides: a single palladium-catalyzed triple relay process.

A novel approach to produce diaryl sulfoxides from aryl benzyl sulfoxides is reported. Optimization of the reaction conditions was performed using high-throughput experimentation techniques. The [Pd(dba)2 ]/NiXantPhos catalyst system successfully promotes a triple relay process involving sulfoxide α-arylation, CS bond cleavage, and CS bond formation.