Highly selective synthesis of primary amines over heterogeneous catalysts is still a challenge for the chemical industry. Ruthenium nanoparticles supported on NbO act as a highly selective and reusable heterogeneous catalyst for the low-temperature reductive amination of various carbonyl compounds that contain reduction-sensitive functional groups such as heterocycles and halogens with NH and H and prevent the formation of secondary amines and undesired hydrogenated byproducts. The selective catalysis of these materials is likely attributable to the weak electron-donating capability of Ru particles on the NbO surface. The combination of this catalyst and homogeneous Ru systems was used to synthesize 2,5-bis(aminomethyl)furan, a monomer for aramid production, from 5-(hydroxymethyl)furfural without a complex mixture of imine byproducts.

A rhodium-catalyzed silylation reaction of carbon-cyano bonds using disilane has been developed. Under these catalytic conditions, carbon-cyano bonds in aryl, alkenyl, allyl, and benzyl cyanides bearing a variety of functional groups can be silylated. The observation of an enamine side product in the silylation of benzyl cyanides and related stoichiometric studies indicate that the carbon-cyano bond cleavage proceeds through the deinsertion of silyl isocyanide from eta(2)-iminoacyl complex B. Knowledge gained from these studies has led to the development of a new intramolecular biaryl coupling reaction in which aryl cyanides and aryl chlorides are cross-coupled.

Characteristic features of the positron binding structure of some nitrile (-CN functional group) species such as acetonitrile, cyanoacetylene, acrylonitrile, and propionitrile are discussed with the configuration interaction scheme of multi-component molecular orbital calculations. This method can take the electron-positron correlation contribution into account through single electronic-single positronic excitation configurations. Our PA value of acetonitrile with the electronic 6-31++G(2df,2pd) and positronic [15s15p3d2f1g] basis set is calculated as 4.96 mhartree, which agrees to within 25% with the recent experimental value of 6.6 mhartree by Danielson et al. [Phys. Rev. Lett., 2010, 104, 233201]. Our PA values of acrylonitrile and propionitrile (5.70 and 6.04 mhartree) are the largest among these species, which is consistent with the relatively large dipole moments of the latter two systems.

The reaction of aryl cyanides with diboron in the presence of a rhodium/Xantphos catalyst and DABCO affords arylboronic esters via carbon-cyano bond cleavage. This unprecedented mode of reactivity for a borylrhodium species allows the regioselective introduction of a boryl group in a late stage of synthesis.

A rhodium-catalyzed coupling reaction of 2-trimethylsilylphenylboronic acid with internal alkynes is developed for the synthesis of 2,3-disubstituted benzosilole derivatives. A range of functional groups, encompassing ketones, esters, amines, aryl bromides, and heteroarenes, are compatible, which provides rapid access to diverse benzosiloles. Sequential 2-fold coupling enables modular synthesis of asymmetrically substituted 1,5-dihydro-1,5-disila-s-indacene, a π-extended molecule of interest in organic electronics. In terms of the mechanism, the reaction involves cleavage of a C(alkyl)-Si bond in a trialkylsilyl group, which normally requires extremely harsh conditions for activation. Mechanistic studies, including effects of substituents, reveal that C-Si bond cleavage does not proceed through a hypercoordinated silicon species, but rather through a rhodium-mediated activation process. The potential use of the reaction in catalytic asymmetric synthesis of Si-chiral benzosiloles is also demonstrated.