Nickel complexes hydrolysis

A proline derived chiral nickel complex 1 may be used instead of oe,/J-unsaturated esters of lactones modified with a chiral alcohol as the Michael acceptor. The a,(9-unsaturated acid moiety in 1 reacts with various enolates to afford complexes 2 with diastereomcric ratios of 85 15 to 95 5. Hydrolysis of the imine moiety yields the optically active /(-substituted r-alanines. A typical example is shown296. 

Salmonella typhimurium, 6,582 esters, nickel(II) complexes hydrolysis, 6, 424... 

Most studies on nickel-catalyzed domino reactions have been performed by Ikeda and colleagues [287], who observed that alkenyl nickel species, obtained from alkynes 6/4-41 and a (jr-allyl) nickel complex, can react with organometallics as 6/4-42. If this reaction is carried out in the presence of enones 6/4-43 and TM SCI, then coupling products such as 6/4-44 are obtained. After hydrolysis, substituted ketones 6/4-45 are obtained (Scheme 6/4.12). With cyclic and (5-substituted enones the use of pyridine is essential. Usually, the regioselectivity and stereoselectivity of the reactions is very high. On occasion, alkenes can be used instead of alkynes, though this is rather restricted as only norbornene gave reasonable results [288]. 

Here, one has essentially the case of precipitation of hydrated nickel hydroxide. Hydrolysis may be viewed as the displacement of the weak Lewis base H20 by the strongly complexing OH- ion. 

Early attempts at an asymmetric hydroalumination utilized a chiral -butylsalicylidenime complexed to a nickel(n) complex 117.128 When racemic 3,7-dimethyl-1-octene 116 was treated with 0.2mol% of the nickel complex 117 and 0.3 equiv. of TIBA at 0°C, followed by hydrolysis, the alkene 118 with 1.2% ee was obtained. The unreacted olefin 119 was recovered and found to have an ee of 1.8% (Scheme 14). 

For other examples of the use of volume profiles, see Refs. 171 (base hydrolysis of CofNHjljX" ), 172 (nickel complexing with glycolate and lactate) and general reviews. 

In recent years there has been considerable interest in the reactions of nitriles in the coordination sphere of metal ions. Breslow et al.312 first reported that the hydrolysis of 2-cyano-l,10-phenanthro-line to the corresponding carboxamide is strongly promoted by metal ions such as copper(II), nickel(II) and zinc(II). Base hydrolysis of the 1 1 nickel complex is 107 times faster than that of the uncomplexed substrate. The entire rate acceleration arises from a more positive value of AS. Somewhat similar effects have been observed for base hydrolysis of 2-cyanopyridine to the corresponding carboxamide. In this case rate accelerations of 109 occurred with the nickel(II) complex.313... 

Ni(0) catalyst. A radical 5-exo cyclization to the potentially zinc or nickel-complexed ketone provides an alkoxyl radical that combines with the co-produced Ni(I) species. A transmetalation to a zinc alkoxide regenerates the catalyst and forms the zinc cyclopentoxide, from which products 79 are liberated on hydrolysis. A bimetallic Cu(I)-Mn(II) system provided similar results (see Sect. 8.4). Analogous samarium diiodide-mediated reactions require in contrast stoichiometric amounts of the reducing agent and are less diastereoselective [26, 27],... 

As an unexpected result of our investigations on the arylation of amines, a new catalysis with nickel complexes was pointed out for the aminolysis of nitriles indeed, in the reaction of the p-bromobenzonitrile with the 4-phenylpyridine in the presence of catalytic amounts of NiBr2, in addition to the expected arylamine, the amide resulting from the aminolysis of the cyano group (and subsequent hydrolysis during the work-up) was isolated (eqn. 8). 

The displacement of the heavy ligand by the lighter molecule HCN yields an increase in the sensitivity, a concept identified as "mass amplification", and was not applied to piezoelectric detectors before. As mass is lost from the coated crystal when exposed to HCN, the frequency increases whereas a decrease in frequency is expected if moisture is absorbed by the coating. The effect of humidity was studied over the range of 40-92% RH, and it was shown that humidity plays a part in the reacation. Since the reaction is irreversible and the nickel complex is prone to hydrolysis, the coated crystal could be used once only. Substitution of other ligands in nickel complexes, including dibenzoylmethane, dipivaloyl-methane, formate and acetate, did not improve the selectivity towards HCN. 

The hafnium complexes 9 and 16, respectively, with their preformed 1,3,5-triphosphinine ligands, are suitable substrates for the preparation of the nickel complex 24 [29]. In addition to the complexes with 7] -coordination, a platinum complex with fj -coordination is known. Complex 25, characterized spectroscopically in solution, undergoes hydrolysis with oxidation of the phosphorus atoms of the triphosphinine to afford the f] -platinum complex 26 possessing a hexahydrotriphosphinine ligand in the boat form as demonstrated by an X-ray crystallographic analysis [30]. 

Addition of allene followed by t-butyl isocyanide to the dodecatrienyl nickel complex (40) gave, after hydrolysis, a mixture of products including several isomers of... 

The free A-aryl-l-isoquinolone molecule can be obtained by hydrolysis of the carbonylated nickel complex shown in Equation (6). 

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