Reductive amination, description

The next milestone came with the description of the condensation reactions between 1,3- dicarbonyl compounds and alcohols, amines or thiol derivatives. This reaction was a great success in the search for simplicity as an efficient tool for green chemical processes, thanks to the reduction of the number of synthetic steps and... 

The transition metal catalyzed synthesis of arylamines by the reaction of aryl halides or tri-flates with primary or secondary amines has become a valuable synthetic tool for many applications. This process forms monoalkyl or dialkyl anilines, mixed diarylamines or mixed triarylamines, as well as N-arylimines, carbamates, hydrazones, amides, and tosylamides. The mechanism of the process involves several new organometallic reactions. For example, the C-N bond is formed by reductive elimination of amine, and the metal amido complexes that undergo reductive elimination are formed in the catalytic cycle in some cases by N-H activation. Side products are formed by / -hydrogen elimination from amides, examples of which have recently been observed directly. An overview that covers the development of synthetic methods to form arylamines by this palladium-catalyzed chemistry is presented. In addition to the synthetic information, a description of the pertinent mechanistic data on the overall catalytic cycle, on each elementary reaction that comprises the catalytic cycle, and on competing side reactions is presented. The review covers manuscripts that appeared in press before June 1, 2001. This chapter is based on a review covering the literature up to September 1, 1999. However, roughly one-hundred papers on this topic have appeared since that time, requiring an updated review. 

Heischer et al. [172] measured the interfacial tension reductirai credited to the complexation between carboxy-terminated PBD and amine-terminated PDMS, which were added to an immiscible blend of PBD and PDMS. The changes in interfacial tensimi resembled the behavior observed for block copolymer addition to homopolymer blends there is initially a linear decrease in interfacial tension with the concentration of functional homopolymer up to a critical concentration, at which the interfacial tension becomes invariant to further increases in the concentration of functional material. However, the formation of interpolymer complexes depends on the equilibrium between associated and dissociated functional groups and, thus, the ultimate plateau value for interfacial tension reduction is dependent on the functional group stoichiometry. A reaction model for end-complexation was developed in order to reproduce the interfacial tension reduction data with Fourier transform infrared spectroscopy applied to determine the appropriate rate constants. The model provided a reasonable qualitative description of the interfacial tension results, but was not able to quantitatively predict the critical compositions observed experimentally. 

The Kindler variation, - which promises to be more useful than the original Willgerodt procedure, consists in heating the ketone with approximately equimolecular amounts of sulfur and a dry amine instead of aqueous ammonium polysulfide. A thioamide is formed as the principal product and on hydrolysis with acid or alkali affords the carboxylic acid, usually in good yield. Generally a secondary aliphatic amine but sometimes a primary amine or even anhydrous ammonia is used the development of a method for the electrolytic reduction of the thioamides to amines extended the usefulness of the reaction as a new route to the synthesis of many important nitrogen bases. Early descriptions of this... 

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