Phosphazenes alkylation reactions

A characteristic feature of this solid-phase amino acid synthesis is the use of the phosphazene bases 53 and 54 for the PTC alkylation reaction [64, 65]. Because these compounds, which are soluble in organic media, do not react with alkyl halides, both alkyl halide and phosphazene bases can be added together at the start of the reaction, which is useful practically [65], Cinchonine and cinchonidine-derived salts, e.g. 25, were found to be very efficient catalysts. Under optimum conditions the alkylation proceeds with enantioselectivity in the range 51-99% ee, depending on the alkyl halide component [65], Seventeen different alkyl halides were tested. After subsequent hydrolysis with trifluoroacetic acid the corresponding free amino acids were obtained in high yield (often >90%). 

The structurally novel bicyclic oxazinone was prepared based on D-glucopyranose. The lithium enolates of these compounds undergo highly diastereoselective alkylation reactions with reactive alkyl halides, in modest yields. Use of the phosphazene P4 base enhanced the yields of these processes, suggesting that metal enolate aggregation is at least partly... 

B. From Cyano-compounds and Phosphorus(v) Halides.—Continued reports of the reactions of alkyl cyanides with phosphorus pentachloride appear. With dicyanides the formation of phosphazenes occurs via a series of intermediates whose stability varies with the nature of X ... 

These A -acyl phosphazenes also decompose further on heating to PhaMePO and RCN. The elimination of methyl iodide probably occurs by a course closely related to the elimination of alkyl halides in the Arbusov reaction, where the alkoxy-group undergoes nucleophilic attack by halide ion. 

The scope of the reactions of phosphazenes with alkyl halides and, subsequently, water, as a preparative route to secondary amines (as their hydrohalides) has been investigated ... 

Derivatization reactions. In addition to changing the substituents in the primary precursor phosphines, (MegSi)2NPRR , two other approaches have been used to prepare polymers with more complex substituents attached to the backbone by direct P-C linkages. These are (a) alteration of R and R in the immediate N-silylphosphoranimine precursors, MegSiN=P(OOUCFo)RR , and (b) alteration of R and R in the preformed poly(alkyl/aryl-phosphazenes), (RR P=N]n. Some examples of the former method are described below and in other papers (21-23), while the use of the latter approach to prepare several silylated poly(alkyl/arylphosphazenes) has been recently reported. (20)... 

Alkyl lithium reagents react with the hydridophosphazenes to generate phosphazeno anions [241]. These anions undergo facile reactions with non-metal halides or alkyl halides to produce phosphazenes with the phosphorus... 

Thus reaction with alkyl halides such as allyl bromide or pro-pargyl bromide allow for the introduction of oleflnlc2. . or acetylenic side groups onto the phosphazene ring VI, while alcohol leads to the formation of hydrido-phosphazene complexes VII. The hydrogen in these compounds can be replaced with halogen to yield the first series of iodor-phosphazene compounds VIII. 

The highly hindered phosphazene base 85, termed P4-f-Bu, is one of a family of similar compounds introduced by Schwesinger, which are completely non-nucleophilic and are useful in performing alkylation and elimination reactions.50-52 Its use in the latter application is illustrated in Protocol 22 by the... 

The oxidation of the alcohol was performed with supported perruthenate (8.48, Fig. 8.46) to produce clean aldehydes 8.91 after filtration. The Henry reaction was performed in the presence of a commercially available, supported strong base 8.92 and an excess of volatile nitroalkenes, giving clean nitroalcohols 8.93 after filtration and evaporation. The reaction mixtures from the trifluoroacetylation/elimina-tion steps were purified with commercially available amino PS resin 8.58 to scavenge the trifluoroacetates and with acidic ion-exchange resin 8.76 to remove the TEA-derived salts. Again, the nitrostyrenes 8.94 were obtained cleanly after filtration and evaporation. Cycloaddition with isocyanoacetate was promoted by the commercially available, supported guanidine base 8.95, while the subsequent N-alkylation of the pyrroles 8.96 was performed with an excess of halide in the presence of the commercially available, supported phosphazene 8.97. In this case, the excess halide was removed by treatment with supported 8.58, and filtra-... 

Reactions of acyclic phosphazenes continue to prove of value in the synthesis of new materials especially in the area of organic chemistry. Reactions in which the phosphazene unit is transformed will be considered first followed by reactions in which the phosphazene unit stays intact. The phosphazenes are usually prepared by the Staudinger reaction. The diversity of reactivity of phosphazenes such as PhN=PPh2CH=C(NH2)C H -p-Me in interactions with electrophiles is shown by reactions with protons or alkyl halides which give phosphonium salts (N-alkylation or protonation). presence of bases, alkylation of the enamlne occurs. 

Amino, alkoxy, and aryloxy polyphosphazenes are typically prepared by nucleophilic displacement reactions of poly(dihalophosphazenes). Analogous reactions with organometallic reagents, however, result in chain degradation and cross linking rather than in linear, alkyl, or aryl substituted poly(phosphazenes). The thermolysis of appropriate silicon-nitrogen-phosphorus compounds can be used to prepare fully P—C bonded poly(organophosphazenes). The synthesis of two of these materials and their Si—N—P precursors is described here. 

The reactions of phosphazenes (prepared in situ from aminophosphonium salts and triethylamine) with sulphur tetrafluoride have been further explored. An example is shown in reaction (3), where X is a bridging alkyl or aryl group. However, when X... 

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