Metal-organic porous materials are receiving growing attention [1] because of their potential applications in gas storage, [2] separation, [3] and many other areas. [4] Although catalysis is one of the most promising applications of such materials, only a handful of examples have been reported to date. [5] Furthermore, despite considerable efforts, attempts to synthesize robust, homochiral metal-organic porous materials capable of enantioselective separation and/or catalysis have met with only limited success. [6,7] Most homochiral metalorganic frameworks are not robust enough to show permanent porosity, nor porous enough to be useful for selective sorption or catalytic transformation of organic molecules. Therefore, the synthesis of robust homochiral metal-organic frameworks with potential for application is still challenging. For the synthesis of homochiral metal-organic open frameworks, two general approaches have been taken: 1) use of a rigid homochiral organic ligand as a spacer to link adjacent metal centers or secondary building units (SBUs), [5b-d, 7] and 2) use of a homochiral ligand as an auxiliary pendant which does not directly participate in the formation of a framework backbone, but forces the framework to adopt a specific chiral topology.[3d] Herein, we introduce another rational approach to the synthesis of homochiral metal-organic frameworks. A metal ion and a readily available homochiral organic ligand are used to form homochiral SBUs, which in turn, are linked together by rigid spacers to build a network structure, in a one-pot reaction (Scheme 1).[8] With a judicious choice of metal ion, homochiral organic molecule, and rigid polytopic linker (that is, a connector with more than one metal coordination site), this approach allows us to synthesize metal-organic open frameworks with stable chiral pores. Herein, we report a new homochiral metal-organic material that has permanent porosity, size-and enantioselective sorption properties, and catalytic activity.[9]

(R)- and (S)- enantiomers of alkyl aryl sulfoxides can be obtained by chromatographic resolution of the racemic mixtures of the sulfoxides on a microporous homochiral Zn-organic polymer or by simultaneous catalytic oxidation of the corresponding sulfides with H2O2 and enantioselective chromatographic resolution of the resulting sulfoxides in a one-pot process.

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The catalytic properties of sulfided Mo/Al2O3, CoMo/Al2O3 and NiMo/Al2O3 catalysts in the hydrodeoxygenation of methyl palmitate as a model compound for triglyceride feedstock were studied at 300 °C and 3.5 MPa in the batch reactor using n-tetradecane, m-xylene and hydrotreated straight-run gas oil (HT-SRGO). The comparison of catalyst's performance in n-tetradecane allowed us to see that the sulfided Mo/Al2O3, CoMo/Al2O3 and NiMo/Al2O3 catalysts revealed the same rate of the methyl palmitate conversion but the rate of the intermediate oxygenates conversion decreased in order: CoMoS/Al2O3 > NiMoS/Al2O3 > MoS2/Al2O3. A mixture of linear saturated and unsaturated C15 and C16 hydrocarbons was produced when the oxygenates were fully consumed. The main products obtained over the Mo/Al2O3 and CoMo/Al2O3 catalysts were C16 hydrocarbons (C16/C15 – 16.1 and 2.79, respectively); however, C15 hydrocarbons were preferentially formed over the NiMo/Al2O3 catalyst (C16/C15 – 0.65), highlighting the different contributions of the hydrodeoxygenation (HDO) and decarboxylation/decarbonylation (DeCOx) pathways during the hydroconversion of methyl palmitate over these catalysts. Investigating the solvent's influence on the activity of the CoMo/Al2O3 and NiMo/Al2O3 catalysts in the methyl palmitate HDO revealed that the reaction rate was decreased in the following order: n-tetradecane > HT-SRGO > m-xylene. The aromatic compounds did not retard the methyl palmitate transformation, but inhibited the conversion of the intermediate oxygenates. Decreased C16/C15 ratios were observed over both catalysts when m-xylene was used as the reaction medium instead of n-tetradecane.

Metal-organic porous materials are receiving growing attention [1] because of their potential applications in gas storage, [2] separation, [3] and many other areas. [4] Although catalysis is one of the most promising applications of such materials, only a handful of examples have been reported to date. [5] Furthermore, despite considerable efforts, attempts to synthesize robust, homochiral metal-organic porous materials capable of enantioselective separation and/or catalysis have met with only limited success. [6,7] Most homochiral metalorganic frameworks are not robust enough to show permanent porosity, nor porous enough to be useful for selective sorption or catalytic transformation of organic molecules. Therefore, the synthesis of robust homochiral metal-organic frameworks with potential for application is still challenging. For the synthesis of homochiral metal-organic open frameworks, two general approaches have been taken: 1) use of a rigid homochiral organic ligand as a spacer to link adjacent metal centers or secondary building units (SBUs), [5b-d, 7] and 2) use of a homochiral ligand as an auxiliary pendant which does not directly participate in the formation of a framework backbone, but forces the framework to adopt a specific chiral topology.[3d] Herein, we introduce another rational approach to the synthesis of homochiral metal-organic frameworks. A metal ion and a readily available homochiral organic ligand are used to form homochiral SBUs, which in turn, are linked together by rigid spacers to build a network structure, in a one-pot reaction (Scheme 1).[8] With a judicious choice of metal ion, homochiral organic molecule, and rigid polytopic linker (that is, a connector with more than one metal coordination site), this approach allows us to synthesize metal-organic open frameworks with stable chiral pores. Herein, we report a new homochiral metal-organic material that has permanent porosity, size-and enantioselective sorption properties, and catalytic activity.[9]

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Various secondary aromatic amines were synthesized by Au/Al2O3-catalyzed one-pot reductive amination of aldehydes with nitroarenes in a flow reactor.