Amine anions oximes

Four-coordinate neutral complexes with anionic ligands derived from deprotonated amines, imines, oximes and related ligands... 

Reductive amination ol aldehydes or ketones by cyanoborohydride (or tnacetoxyborohydride) anion Selective reduction of carbonyls to alcohol, oximes to N alkylhydroxylarmnes, enamines to amines... 

Imanaka—heterogenization of Rh complexes. In 1991, Imanaka and coworkers124 reported the heterogenization of Rh complexes by binding them to aminated polymers. As discussed previously, these findings led to fruitful research by Ford, Pardey, and others. The isolated polymer-bound Rh carbonyl anion complex was found to be reusable for reactions such as water-gas shift and reduction of nitro compounds. The polymer-bound Rh complexes were characterized by infrared spectroscopy. Water-gas shift activity (80 mol H2 per mol Rh6(CO)i6 in 24 hours) was recorded using the Rh complexes at 100 °C with 0.92 atm of CO, 2.16 ml H20, 0.05 mmol Rh6(CO)16, aminated polystyrene, 5.0 mmol of N, 5.56 ml ethoxyethanol and reduction of nitro-compounds (e.g., aliphatic nitro compounds to nitriles, oximes to nitriles, hydroxylamines to nitriles, and N-oxides to amines) occurred at 40 °C. 

A further example of the use of a chiral anion in conjunction with a chiral amine was recently reported by Melchiorre and co-workers who described the asymmetric alkylation of indoles with a,P-unsaturated ketones (Scheme 65) [212]. The quinine derived amine salt of phenyl glycine (159) (10-20 mol%) provided the best platform with which to perform these reactions. Addition of a series of indole derivatives to a range of a,P-unsaturated ketones provided access to the adducts with excellent efficiency (56-99% yield 70-96% ee). The substrates adopted within these reactions is particularly noteworthy. For example, use of aryl ketones (R = Ph), significantly widens the scope of substrates accessible to iminium ion activation. Expansion of the scope of nucleophiles to thiols [213] and oximes [214] with similar high levels of selectivity suggests further discoveries will be made. 

Hydrolysis Oxidation Photolysis Esters, lactones, amides, lactams, oximes, imides, and malonic ureas Amines, sulfides, disulfides, sulfoxides, phenol anions, thiols, nitriles, and catechols Aromatic hydrocarbons, aromatic heterocyclics, aldehydes, and ketones... 

Arylamines.1 A novel method for amination of organometallic reagents involves activation of an O-tosylhydroxylamine by attachment to an auxiliary group that can be recycled. Thus aryl Grignard or lithium reagents react with the O-tosylate oxime of tetraphenylcyclopentadienone (1) to form an imine (2) with elimination of the tosylate anion. The imine is then converted into an ary lamine and the original oxime by treatment with excess hydroxylamine in aqueous pyridine. 

Sulfhydryl groups attached to polymers are easily ionized to form the nucleophilic anionic form in cationic domains, manifesting enhanced reactivity toward labile esters. When labile esters are used as substrates, acylation of the amines, oximes, or sulfhydryls forms intermediates which are more stable than the ester substrates, seldom leading to overall catalysis in the ester hydrolysis. 

Experiments described in this section generally utilize LIX 64N (Henkel Corp.), LIX 54 (Henkel Corp.), and Kelex 100 (Sherex Chemical Co.) oximes, used in the counter transport of copper and other metal cations by the mechanism shown in Figure 9.6, or Alamine 336 (Henkel Corp.), a tertiary amine used in the co-transport of anions by the mechanism shown in Figure... 

In the examples given above to illustrate coupled transport, various oxime carriers for copper and other cations and tertiary amines as carriers for uranyl anions were used. However, a large number of complexing agents have been described in the literature some of them are listed in Table 9.1. 

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