Copper‐Catalyzed Tandem Synthesis of Functionalized Sulfonyl‐yn‐imines from Sodium Arylsulfinates,Trichloroacetonitrile, and Terminal Alkynes

A one‐pot synthesis of functionalized sulfonyl‐yn‐imines via a Cu‐catalyzed tandem reaction of sodium arylsulfinates, trichloroacetonitrile, and terminal alkynes has been developed.     

Thia-Fries rearrangement of aryl triflinates to trifluoromethanesulfinylphenols

Aryl triflinates are transformed to trifluoromethanesulfinylphenols in the presence of aluminum trichloride in dichloromethane at room temperature according to a thia-Fries rearrangement process. Rigorous exclusion of oxygen is necessary in order to avoid the formation of 2,2′-dihydroxybiaryls as secondary products.     

Generation and Use of Glycosyl Radicals under Acidic Conditions: Glycosyl Sulfinates as Precursors

We herein report a method that enables the generation of glycosyl radicals under highly acidic conditions. Key to the success is the design and use of glycosyl sulfinates as radical precursors, which are bench-stable solids and can be readily prepared from commercial starting materials. This development allows the installation of glycosyl units onto pyridine rings directly by the Minisci reaction. We further demonstrate the utility of this method in the late-stage modification of complex drug molecules, including the anticancer agent camptothecin. Experimental studies provide insight into the reaction mechanism.     

Highly stereoselective and catalytic desulfitative CO and CI dienylation with sulfolenes: The importance of basic additives

Conjugated dienes and polyenes are central structural motifs of natural products, and key synthetic intermediates in organic synthesis and materials science. We describe herein a palladium-catalyzed dienylation of aryl, heteroaryl, and vinyl triflates, nonaflates and iodides that were previously identified as recalcitrant substrates for the sulfolene-mediated catalytic dienylation. The method has now been successfully expanded to CO and CI dienylation, demonstrating broad scope with respect to sulfonates, iodides and sulfolenes. The reactions proceed with high regio- and stereoselectivity, and efficiency that are strongly influenced by basic additives, whose influence on the reaction performance was systematically studied.     

Coordination of Phenylsulfinate PhSO2— to Mo3MS44+ Clusters (M = Ni,Pd)

Reaction of heterometal cuboidal clusters [Mo₃(MCl)S₄(H₂O)₉]³⁺ (M = Ni, Pd) with PhSO₂Na in aqueous HCl leads to the substitution at Ni or Pd to give the [Mo₃(M(PhSO₂))(H₂O)_9—xCl_x]^(3—x)+species, isolated as supramolecular adducts with cucurbituril (Cuc) [Mo₃(Ni(PhSO₂))S₄Cl_1.17(H₂O)_7.83][Mo₃(Ni(PhSO₂))S₄Cl_2.22(H₂O)_6.78]Cl_2.61 · Cuc · 15H₂O ( 1 ) and [Mo₃(Pd(PhSO₂))S₄Cl_1.12(H₂O)_7.88][Mo₃(Pd(PhSO₂))S₄Cl_2.29(H₂O)_6.71]Cl_2.59 · Cuc · 11H₂O ( 2 ), respectively. Crystal structure of 1 and 2 was determined, revealing that the PhSO₂ is coordinated via its sulfur atom (Ni — S 2.182 Å, Pd — S 2.305 Å). The structure of these isostructural compounds is built from triple aggregates {(cluster)(Cuc)(cluster)} united into zigzag chains via hydrogen bonds between coordinated PhSO₂ and H₂O ligands.