Amines, organometallic

Maddock SM, Finn MG (2000) Palladium-catalyzed head-to-head telomerization of isoprene with amines. Organometallics 19 2684—2689... 

Winter, R. F., Hornung, F. M. The Aza-Cope Rearrangement in Transition Metal Complexes. Construction of an Unsaturated C7-Ligand from Butadiyne and an Allylic Amine. Organometallics 1997, 16, 4248 250. 

Literature data confirm the possibilities of complexation between reagents (isocyanate, alcohol) and catalyst (tertiary amine, organometallic compound) considered two by two. 

Inhibition of cure is caused by various widley used substances such as sulfijr compounds, amines, organometallic compounds, unsaturated hydrocarbons etc. 

From To - Alkanes Cycloalkanes Alkenes Alkynes Aryls Halogen compounds Alcohols Phenols Ethers, Quinones B. and Si compounds P and 6i compounds Nitro, Nitroso, Azo, Azoxy, Hydrazo, ides Amines Organometallic Aldehydes Ketones Acids, Anhydrides, Esters Arn.des, Amidines, Nitriles Hydroky-aldehydes Amino Heterocycles Nucleosides Miscellaneous, including heterocycles... 

The reaction may be of some preparative interest for obtaining alkylbenzonitriles and various a-functionalized alkylbenzonitriles starting from polynitriles (see Scheme 4.10 and Scheme 4.11) [56,57]. Donors that can be conveniently used as the precursors of the radicals include Jt donors, such as alkenes [58,59] and alkyl aromatics [60-63], heteroatom-centered donors, such as carboxylic acids [64] and ierf-butyl esters [65], ethers [66], ketals [67] (as well as cyclopropanone sUyl ketals) [68] and amines, organometallic donors such as silanes, silyl ethers, and silyl amines [69-71] as well as germanes, stannanes, and borates [72]. 

Piechaczyk O, Doux M, Ricard L, Le Floch P (2005) Synthesis of 1-phosphabarrelene phosphine sulfide substituted palladium(ll) complexes application in the catalyzed suzuki cross-coupling process and in the allylation of secondary amines. Organometallics 24 1204—1213... 

Zirconium tetrachloride is instantly hydrolyzed in water to zirconium oxide dichloride octahydrate [13520-92-8]. Zirconium tetrachloride exchanges chlorine for 0x0 bonds in the reaction with hydroxylic ligands, forming alkoxides from alcohols (see Alkoxides, METAl). Zirconium tetrachloride combines with many Lewis bases such as dimethyl sulfoxide, phosphoms oxychloride and amines including ammonia, ethers, and ketones. The zirconium organometalLic compounds ate all derived from zirconium tetrachloride. 

Although inhibitors are deliberately added to the silicone formulation to control cure rate, unwanted cure inhibition can be caused by other species that react to form strong complexes with the platinum catalyst. Most notable of these undesired inhibitors include organotin and other organometallic compounds, sulfur, polysulfides, polysulfones or other sulfur-containing materials, amines, urethanes or amine-containing materials, unsaturated hydrocarbons in plasticizers, and some solder flux residues. 

Low surface energy substrates, such as polyethylene or polypropylene, are generally difficult to bond with adhesives. However, cyanoacrylate-based adhesives can be effectively utilized to bond polyolefins with the use of the proper primer/activa-tor on the surface. Primer materials include tertiary aliphatic and aromatic amines, trialkyl ammonium carboxylate salts, tetraalkyl ammonium salts, phosphines, and organometallic compounds, which are initiators for alkyl cyanoacrylate polymerization [33-36]. The primer is applied as a dilute solution to the polyolefin surface, solvent is allowed to evaporate, and the specimens are assembled with a small amount of the adhesive. With the use of primers, adhesive strength can be so strong that substrate failure occurs during the course of the shear tests, as shown in Fig. 11. 

The scheme used above for attaching the side chain is not applicable to secondary amines since such compounds would not form organometallics. In an ingenious synthesis, the ketone,... 

Nitriles are similar in some respects to carboxylic acids and are prepared either by SN2 reaction of an alkyl halide with cyanide ion or by dehydration of an amide. Nitriles undergo nucleophilic addition to the polar C=N bond in the same way that carbonyl compounds do. The most important reactions of nitriles are their hydrolysis to carboxylic acids, reduction to primary amines, and reaction with organometallic reagents to yield ketones. 

The most common reactions of carboxylic acid derivatives are substitution by water (hydrolysis) to yield an acid, by an alcohol (alcoholysis) to yield an ester, by an amine (aminolysis) to yield an amide, by hydride ion to yield an alcohol (reduction), and by an organometallic reagent to yield an alcohol (Grignard reaction). 

In the case of the amide 11 (R = CI13) derived from 2-oxopropanoic amid and amine G the chelation-controlled product is predominantly formed with all organometallic reagents. No reversal of the stereochemistry is observed, presumably for the same steric reason as with the corresponding pyruvic amides derived from amines E and F. 

The addition of organometallic reagents to the C —N double bond of imines 1 provides an attractive route to amines 21 2. However, due to the poor electrophilici ty of imines, this method is often plagued by competitive reactions ... 

Addition of Grignard and organolithium reagents to imines 2. derived from enantiomerically pure (S)-valinol (1), provides a-substituted phenethylamines 3 in moderate to good yield and excellent diastereoselectivity (in each case only one diastereomer can be detected by NMR)15. By appropriate selection of imine and organometallic reagent both diastereomeric amines are accessible (see also refs 16 and 17). 

Addition of organometallics to hydrazones provides hydrazines1, which can be converted to the corresponding amines by hydrogenolysis. Hydrazones can therefore be regarded as masked imine derivatives of ammonia. This methodology has been utilized successfully for numerous stereoselective syntheses of amines and amine derivatives2-23. 

Table 4. Addition of Organometallics to Chiral /V,jV-Dimethyl Hydrazone Aminals Sb6,7 HsCe,...

The synthesis of alkoxy amines 2 by addition of organometallic reagents to the C-N double bond of oxime ethers 1 is plagued by the propensity for proton abstraction a. to the C-N double bond, the lability of the N-O bond and the poor electrophilicity of the oxime ethers. Therefore, frequently no products, undesired products or complex mixtures are obtained. The result depends on the substrate, organometallic reagent, solvent, temperature and additives1 6. 

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