Magnetically recoverable nickel-palladium alloy nanocatalysts for direct C-H arylation reactions.

Novel magnetically recoverable nanocatalyst comprising nickel-palladium (NiPd) alloy nanoparticles (NPs) supported on reduced graphene oxide (rGO) modified with cobalt ferrite (CoFe2O4) NPs was fabricated for the direct C-H arylation of imidazopyridine, imidazole, indolizine and furan with aryl halides. To prepare the presented catalyst, rGO nanosheets were first modified with as-synthesized CoFe2O4 NPs and then the obtained CoFe2O4-rGO nanocomposites served as a support material for the synthesis of bimetallic NiPd alloy NPs at various compositions. The obtained CoFe2O4-rGO/NiPd nanocatalysts were characterized by many advanced analytical techniques including TEM, STEM-EDS, XRD, XPS, and ICP-MS. Next, to optimize the reaction conditions, CoFe2O4-rGO/NiPd nanocatalysts with different alloy compositions and their monometallic counterparts (CoFe2O4-rGO/Ni and CoFe2O4-rGO/Pd) were initially tested in the direct C-H arylation of imidazopyridine with bromobenzene. Among all tested nanocatalysts under the optimum reaction conditions, CoFe2O4-rGO/Ni20Pd80 showed the best catalytic activity in terms of the isolated product yields. The C-H arylation reactions were studied over a broad substrate scope (35 examples from 36 substrates) and gave the related biaryl products in good to excellent yields. Besides a broad substrate scope, the late-stage C-H arylation of zolimidine, a gastroprotective drug, was realized under the optimized reaction conditions. Moreover, the CoFe2O4-rGO/Ni20Pd80 nanocatalysts were recovered from the reaction medium using a simple magnet and reused in the C-H arylation reactions up to five consecutive runs without a significant drop in the product yield. This study shows that magnetically recoverable Pd nanoalloys are promising heterogeneous catalysts to be used in sustainable C-H functionalization reactions.

Stereoselective syntheses of 3-aminocyclooctanetriols and halocyclooctanetriols.

The efficient synthesis of two new stereoisomeric 3-aminocyclooctanetriols and their new halocyclitol derivatives starting from cis,cis-1,3-cyclooctadiene are reported. Reduction of cyclooctene endoperoxide, obtained by photooxygenation of cis,cis-1,3-cyclooctadiene, with zinc yielded a cyclooctene diol followed by acetylation of the hydroxy group, which gave dioldiacetate by OsO4/NMO oxidation. The cyclooctane dioldiacetate prepared was converted to the corresponding cyclic sulfate via the formation of a cyclic sulfite in the presence of catalytic RuO4. The reaction of this cyclic sulfate with a nucleophilic azide followed by the reduction of the azide group provided the target, 3-aminocyclooctanetriol. The second key compound, bromotriol, was prepared by epoxidation of the cyclooctenediol with m-chloroperbenzoic acid followed by hydrolysis with HBr(g) in methanol. Treatment of bromotriol with NaN3 and the reduction of the azide group yielded the other desired 3-aminocyclooctanetriol. Hydrolysis of the epoxides with HCl(g) in methanol gave stereospecifically new chlorocyclooctanetriols.