For synthesis of amines

Amides are weakly nucleophilic and react only slowly with alkyl halides. The anions of amides are substantially more reactive. The classical Gabriel procedure for synthesis of amines from phthalimide is illustrative.58... 

Figure 9.2 Potential starting materials for synthesis of amine 2.

Sulfonylhydroxylamines and hydroxylamine O-sulfonic acid have found wide apph-cation in synthesis of amines from achiral or chiral organoboranes and boronate esters and the hydroboration-amination methodology is successfully used for direct amination of alkenes. 0-Sulfonyloximes were also found to be good reagents for synthesis of amines from organomagnesium, -copper and -zinc reagents. 

Reduction of amides by LiAlH4 is an important method for synthesis of amines ... 

I. Moritani, T. Hosokawa u. S.I. Murahashi, Organotransition-Met. Chem., Proc. Jpn.-Am. Semin., 1st, 273 -279 (1973) The Palladium-catalyzed Reactions for Synthesis of Amines and Benzofurans". 

In spite of the relatively low performance/cost ratio of the respective products, application of reactions on polymers are of continuous interest for synthesis of amine functionalized polymers. The technique of modification of solid polymers by exploitation of their reactive moieties under heterogeneous conditions allows properties to be tailored and optimized according to specific needs and requirements. Telechelic polymers are used for the synthesis of materials with predictable and controlled properties. Application of carefully designed macromolecules provides systems with functional groups dispersed along the polymer chain or bond at the end of macromolecules. 

Organotransition-Metal Chemistry, Y. Ishii and M. Tsutsui, Eds., Plenum Press, New York, 1975, 273-279. The Palladium Catalyzed Reactions for Synthesis of Amines and Benzofurans. 

Although this reaction is useful for preparing a ammo acids (Table 22 3 fifth entry) it IS not a general method for the synthesis of amines Its major limitation is that the expected primary amine product is itself a nucleophile and competes with ammonia for the alkyl halide... 

In this representation the FeCl2 which takes part in the first step of the reaction is not a tme catalyst, but is continuously formed from HQ. and iron. This is a highly exothermic process with a heat of reaction of 546 kj /mol (130 kcal/mol) for the combined charging and reaction steps (50). Despite the complexity of the Bnchamp process, yields of 90—98% are often obtained. One of the major advantages of the Bnchamp process over catalytic hydrogenation is that it can be mn at atmospheric pressure. This eliminates the need for expensive high pressure equipment and makes it practical for use in small batch operations. The Bnchamp process can also be used in the laboratory for the synthesis of amines when catalytic hydrogenation caimot be used (51). 

A variation of this procedure is used for sulfisomidine because of the different character of the amino group in the 4-position of a pyrimidine ring. Two moles of the sulfonyl chloride are condensed with one mole of 4-amino-2,6-dimethy1pyrimidine in the presence of triethylamine. The resulting bis(acetylsulfanilyl) derivative is readily hydrolyzed to the product. The formation of the bis(acetylsulfanilyl) derivative has also been employed for other heterocycHc amines, eg, for synthesis of sulfathiazole and sulfamoxole (44), but the 1 1 reaction is probably preferable. 

Monochloramine is also used in organic synthesis for preparation of amines, substituted hydrazines, etc. For example, reaction of NH2CI with 3-azabicyclo [3.3.0]octane [5661-03-0] yields A/-amino-3-azabicyclo[3.3.0]octane [54528-00-6] a pharmaceutical intermediate (38). 

In recent years the solid-phase hydrosilylation reaction was successfully employed for synthesis of hydrolytically stable surface chemical compounds with Si-C bonds. Of special interest is application of this method for attachment of functional olefins, in particular of acrolein and some chiral ligands. Such matrices can be used for subsequent immobilization of a wide range of amine-containing organic reagents and in chiral chromatography. 

The most general method for synthesis of cyclic enamines is the oxidation of tertiary amines with mercuric acetate, which has been investigated primarily by Leonard 111-116) and applied in numerous examples of structural investigation and in syntheses of alkaloids 102,117-121). The requirement of a tram-coplanar arrangement of an a proton and mercury complexed on nitrogen, in the optimum transition state, confers valuable selectivity to the reaction. It may thus be used as a kinetic probe for stereochemistry as well as for the formation of specific enamine isomers. 

For synthesis of the parent isoindole, Kreher and Seubert used the condensation of theo-xylene dibromide (23) with 0-benzylhydroxyl-amine (24) to give 2-henzyloxyisoindoline (25). Elimination occurred 25 A. H. Blatt, Chem. Rev. 27, 429 (1940). 

Tm-mediated-radical cyclizadon of isonitnles provides a usefid strategy for the preparadon of indoles (Tukuyama reacdoni This radical cyclizadon is used for synthesis of 6-hydroxy-indole-3-acetic acid, which is thearomadc subunit of Nephdatoxin The reqidsite isotdtnles are prepared from rdtroarenes via amines fEq 10 66 ... 

The synthesis and mechanism of formation of a triazene from an arenediazonium ion and an amine with one or two aliphatic substituents (see Scheme 13-1, R = alkyl, R = H or alkyl) will be discussed in Section 13.2. Here we will briefly mention Dimroth s method (1903, 1905 a) for synthesis of wholly aliphatic triazenes (Scheme 13-6, R and R = alkyl). Dimroth obtained these by the action of Grignard reagents on alkyl azides followed by isolation via copper(i) salts. The Grignard method can also be applied for the synthesis of triazenes with an aromatic substituent by using an aryl azide. 

Recent efforts in the development of efficient routes to highly substituted yS-ami-no acids based on asymmetric Mannich reactions with enantiopure sulfmyl imine are worthy of mention. Following the pioneering work of Davis on p-tolu-enesulfmyl imines [116], Ellman and coworkers have recently developed a new and efficient approach to enantiomerically pure N-tert-butanesulfmyl imines and have reported their use as versatile intermediates for the asymmetric synthesis of amines [91]. Addition of titanium enolates to tert-butane sulfmyl aldimines and ketimines 31 proceeds in high yields and diastereoselectivities, thus providing general access to yS -amino acids 32 (Scheme 2.5)... 

A great deal of work has been done on the in situ activation of carboxylic acids toward nucleophilic substitution by amines. This type of reaction is fundamental for synthesis of polypeptides (see also Section 13.3.1). Dicyclohexylcarbodiimide... 

Organocerium reagents also show excellent reactivity toward nitriles and imines,205 and organocerium compounds were found to be the preferred organometallic reagent for addition to hydrazones in an enantioselective synthesis of amines.206... 

Hepatic steatosis usually is a result of excessive administration of carbohydrates and/or lipids, but deficiencies of carnitine, choline, and essential fatty acids also may contribute. Hepatic steatosis can be minimized or reversed by avoiding overfeeding, especially from dextrose and lipids.35,38 Carnitine is an important amine that transports long-chain triglycerides into the mitochondria for oxidation, but carnitine deficiency in adults is extremely rare and is mostly a problem in premature infants and patients receiving chronic dialysis. Choline is an essential amine required for synthesis of cell membrane components such as phospholipids. Although a true choline deficiency is rare, preliminary studies of choline supplementation to adult patients PN caused reversal of steatosis. 

Recently, a new method for synthesis of tertiary amines 326 from iV,iV-dialkyl O-benzoyl hydroxylamines 325 was proposed.425 The protocol is based on the copper-catalyzed reaction of hydroxylamines 325 with dialkyl- and diarylzinc reagents (Scheme 166). It is noteworthy that alkyl- and phenylzinc halides also reacted with compounds 325, however, yields were significantly lower than those for ZnR2 (18-29% vs. 69-98%). 

The reactions used for synthesis of II-VI (CdSe, CdTe), III-V (InP, InAs), and IV-VI (PbS, PbSe, PbTe) semiconductor nanocrystals are outlined by Schemes 3-5.4,17,30-32 The syntheses are carried out at high temperatures, and in the presence of long-chain alkylphosphines (trioctylphosphine,TOP), alkyl-phosphine oxides (trioctylphosphine oxide, TOPO), alkylamines (hexadecyl-amine, HD A), and alkylphosphonic acids as the stabilizing agents. 

Asymmetric alkylation. Deprotonation of (-)-l provides exclusively an (E)-enolate, which is alkylated to provide a single diastereomeric product. De-complexation by oxidation [Br, I2, Ce(IV)] in the presence of water provides the corresponding acid with the same configuration. This sequence has been used for synthesis of the drug (- )-captopril (3). In this case liberation of the acyl group in the presence of the amine provides the amide 2. 

Chiral amines.1 These reagents also add to imines and this reaction can be used for synthesis of optically active amines. Thus RCeCl2 adds to SAMP-hydra-zones (12, 30) to form hydrazines in good yield and high diastereoselectivity. These are reduced to optically active amines by hydrogenation catalyzed by Raney nickel. The hydrazines are prone to oxidation, but can be isolated as the stable carbamates. 

---