Hydration, Alcoholation and the Related Reactions of Unsaturated Compounds

Hydration, Alcoholation and the Related Reactions of Unsaturated Compounds 

Catalytic hydration and alcoholation of unsaturated compounds such as alkenes or alkynes would be a high value-adding step in the synthesis of compounds of complicated structure as well as in the large-scale production of industrially useful simple compounds. The activation of the O-H bond of water, alcohol, or carboxylic acid by transihon metals is relevant to a variety of such catalytic processes. 

Among these catalysts, systems obtained by the reaction between trans-[PtH(Cl)(PR3)2] (R = Me and Et) and 1 equiv. of NaOH are the most active [72]. For 

Several cationic palladium(II) aqua complexes, [Pd(H20)4], cis-[PdL(H20)2] (L = en, methionine methyl ester, l,5-dithiacycloocta-3-ol), and [Pd(dien)(H20)], serve as the active catalyst for the selective hydration of various nitriles to the corresponding carboxamides, e.g., CHCI2CN was hydrated to CHCl2C(0)NH2 in the presence of 

We also found that iridium hydrido(hydroxo) complexes like [ IrH(diphos-phine) 2( x-OH)2(ti-Cl)]Cl (43) and the precursor diphosphine complexes 42 can also catalyze the hydration of nitriles. In the presence of catalytic amounts of these complexes, heating acetonitrile and benzonitrile with excess water at 120°C gave the corresponding amides [47, 50]. 

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