In the presence of a manganese oxide based octahedral molecular sieve (OMS-2), a range of primary amides could be synthesized directly from primary alcohols and ammonia. The observed catalysis was heterogeneous, and the recovered catalyst could be reused many times without an appreciable loss of its catalytic performance.
In full support: A supported ruthenium hydroxide, Ru(OH)x/Al2O3, served as an efficient heterogeneous catalyst for the aerobic oxidative synthesis of nitriles directly from primary alcohols (or aldehydes) and ammonia. The retrieved catalyst could be reused without a significant loss of its catalytic performance.
The N-alkylation of ammonia (or its surrogates, such as urea, NH(4)HCO(3), and (NH(4))(2)CO(3)) and amines with alcohols, including primary and secondary alcohols, was efficiently promoted under anaerobic conditions by the easily prepared and inexpensive supported ruthenium hydroxide catalyst Ru(OH)(x)/TiO(2). Various types of symmetrically and unsymmetrically substituted "tertiary" amines could be synthesized by the N-alkylation of ammonia (or its surrogates) and amines with "primary" alcohols. On the other hand, the N-alkylation of ammonia surrogates (i.e., urea and NH(4)HCO(3)) with "secondary" alcohols selectively produced the corresponding symmetrically substituted "secondary" amines, even in the presence of excess amounts of alcohols, which is likely due to the steric hindrance of the secondary alcohols and/or secondary amines produced. Under aerobic conditions, nitriles could be synthesized directly from alcohols and ammonia surrogates. The observed catalysis for the present N-alkylation reactions was intrinsically heterogeneous, and the retrieved catalyst could be reused without any significant loss of catalytic performance. The present catalytic transformation would proceed through consecutive N-alkylation reactions, in which alcohols act as alkylating reagents. On the basis of deuterium-labeling experiments, the formation of the ruthenium dihydride species is suggested during the N-alkylation reactions.
The supported copper hydroxide on titanium oxide (Cu(OH)x/TiO2) has been shown to act as an efficient heterogeneous catalyst for the oxidative alkyne–alkyne homocoupling. A wide variety of alkynes including aromatic, aliphatic, double‐bond‐containing, and silylacetylene derivatives were selectively converted into the corresponding diyne derivatives in high yields without any additives such as bases.
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