Amine chemistry

General amine chemistry is appHcable to fatty amines. Many chemical reactions using fatty amines as reactive intermediates are mn on an industrial scale to produce a wide range of important products. Important industrial reactions are as follows. 

Novel amine chemistry based on 4-(dimethylamino)pyridine-catalyzed acylation 98ACR494. 

Antistatic agents are ionic substances, such as inorganic salts or organic materials, which attract water molecules. Outstanding materials are derived from the fatty amide and amine chemistry, such as ethoxylated alkyl amines, glycerolmonostearate, fatty alkanolamines, and sodium alkylsulfonates (C12-C16 alkyl groups are preferred because of low loss by evaporation). 

The trivalent Co coordination chemistry of amines is simply immense. Amines, both mono- and multidentate, are typically thermally and air stable, often commercially available, easily deriva-tized, and are well matched to the electronic needs of trivalent Co. Space does not permit a discussion of all categories of amines that have been investigated since CCC(1987) nor their limitless permutations when bound to mostly six-coordinate Co. Much of the synthetic and mechanistic work that underpins Co amine chemistry has long been known and will not be restated here. The emphasis here will be on novelty rather than breadth. That is, recent innovative aspects of the structure, reactivity, and applications of selected, but representative, collections of these simple but ever-present compounds will be our focus. 

With the exception of intramolecular amination reactions, all of the early aryl halide aminations were catalyzed by palladium complexes containing the sterically hindered P(o-tol)3. In papers published back-to-back in 1996, amination chemistry catalyzed by palladium complexes of DPPF and BINAP was reported.36,37 These catalysts allowed for the coupling of aryl bromides and iodides with primary alkyl amines, cyclic secondary amines, and anilines. 

W. Jerzykiewicz u. W. Misiumy, Przem. Chem. 66, 67-70 (1987) Review of Fatty Amine Chemistry -New Aspects and Trends in Development". 

Using amine chemistry for reduction and for surface stabilization at the same time, gold nanoparticles can be prepared in water directly by addition of oleyl amine (O LA) to a solution of AuCI4. The XRD measurements show the peaks that confirm the face centered cubic (fee) lattice of gold. The analysis of the obtained nanoparticles displays narrow size distributions and, for example, when high concentrations of oleyl amine are used an average core size of 10 0.6 nm is achieved [79]. 

Desmarets, C. Scheinder, R. Fort, Y. Nickel-mediated amination chemistry. Part 1 Efficient aminations of (het)aryl 1,3-di and 1,3,5-trichloride s. Tetrahedron Lett. 2000, 41, 2875-2879. 

With special regard to CO-bond formation including intra-molecular examples two papers by Buchwald [27] have been published. Recent advances in amination chemistry was highlighted by Buchwald [28] and Hartwig [29]. 

U. Ragnarsson, L. Grehn, Novel Amine Chemistry Based on DMAP-Catalyzed Acylation, Acc. Chem. Res. 1998, 31, 494-501. 

Covalently immobilized arrays are formatted by glycans with functionalized spacers that react with a complementary activated surface to form a covalent bond. Several different covalent interactions were reported to construct a specified glycan array. Amine chemistry and thiol chemistry are the two major methods to conjugate glycans to the reactive substrate in the array surface (Fig. 15.2). Thiol chemistry was first adapted by Injae Shin in 2002 to react with the maleimide functional group (Fig. 15.2a, b) [7,41 ]. Disulfide bond formation was then reported for the fabrication... 

An attractive procedure for allylic amination is the direct electrophilic amination of alkenes. The single-step procedure allows a convenient allylic functionalization, which is an important part of this amination chemistry. However, compared to the nucleophilic amination of functionalized alkenes, the electrophilic amination of nonfunctionalized alkenes is much more complex, both from a synthetic and mechanistic point of view. 

In contrast, few examples of reductive elimination reactions that form the C-N bond in amines are known. Only in the past several years have complexes been isolated that undergo these reactions [49-54]. These reductive eliminations are the crucial C-N bond-forming step of the aryl halide and triflate amination chemistry discussed in this review. Information on how these reactions occur, and what types of complexes favor this process, has been crucial to the understanding and development of new amination catalysts [50],... 

Boger reported studies on palladium-mediated cyclization to form the CDE ring system of lavendamycin, as shown in Eq. (2) [74-76]. These reactions were conducted with stoichiometric amounts of [Pd(PPh3)4] (2). When used in a 1 mol% quantity, 2 failed to catalyze these reactions, presumably because of the absence of a base. Until almost 10 years later, no palladium-catalyzed animation chemistry was reported, and few citations of the early amination chemistry existed. 

DPPF-ligated palladium provided nearly quantitative yields for amination of aryl halides with anilines (Eq. (7)). Electron-rich, electron-poor, hindered or unhindered aryl bromides or iodides all participated in the amination chemistry, with only a few exceptions. Nitro haloarenes gave no amination product with aniline substrates,... 

Studies on the applications of the amination chemistry have begun to emerge. These results demonstrate the utility of the amination in the construction of complex, biologically active molecules, in the synthesis of electronically important structures, and in the synthesis of ligands for other catalytic chemistry. 

The previous sections described synthetic methods involving palladium- and nickel-catalyzed additions of alcohols and amines to aryl halides and triflates. The development of procedures and catalysts used in these processes has occurred hand-in-hand with mechanistic analysis of the amination chemistry. The following sections describe the current understanding of why these procedures and catalysts are effective, and how this understanding led to some of the breakthroughs described above. 

The amination chemistry depends on the absence of irreversible P-hydrogen elimination from the amido complexes before reductive elimination of amine. At the early stages of the development of the amination chemistry, it was remarkable that the unknown reductive elimination of arylamines could be faster than the presumed rapid [57,58] P-hydrogen elimination from late metal amides. In fact, directly-observed P-hydrogen elimination from late metal amido complexes was rare, and no examples were observed to occur irreversibly from a simple monomeric amido species [69], At this point, it is clear that C-N bond-forming reductive elimination of amines and ethers can be rapid, and that P-hydrogen elimination can be slow. 

Two studies have been conducted that outline the effects of ligand steric and electronic properties on the relative rates for reductive elimination of amine and P-hydrogen elimination from amides. One study focused on the amination chemistry catalyzed by P(o-C6H4Me)3 palladium complexes [111], while the second focused on the chemistry catalyzed by complexes containing chelating ligands [88]. 

The amination of aryl halides and triflates catalyzed by palladium complexes is suitable for use in complex synthetic problems. Many substrates will produce high yields of mixed arylamines with one of the existing catalyst systems. Nevertheless, there are many combinations of substrates for which the amination chemistry may be substantially improved. For the most part, these reactions involve nitrogen centers, such as those in pyrroles, indoles, amides, imidazoles and other heterocyclic groups that are less basic than those in standard alkylamines. Although mild reaction conditions have been developed for many substrates, the harsh conditions used in many of the applications indicate that continued studies on developing mild condi-... 

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