Phosphonium salts substitution

In the case of phosphonium salts substituted by an heteroaryl group, the furfuryl group is easily cleaved744 2,4-pyridindiyl bis(phosphonium) salts have been used as source of 2-pyridylphosphonio compounds745 (reaction 221). Clearly, the presence of... 

The addition of P—H bonds across a carbonyl function leads to the formation of a-hydroxy-substituted phosphines. The reaction is acid-cataly2ed and appears to be quite general with complete reaction of each P—H bond if linear aUphatic aldehydes are used. Steric considerations may limit the product to primary or secondary phosphines. In the case of formaldehyde, the quaternary phosphonium salt [124-64-1] is obtained. 

Although unsynunetrically substituted amines are chiral, the configuration is not stable because of rapid inversion at nitrogen. The activation energy for pyramidal inversion at phosphorus is much higher than at nitrogen, and many optically active phosphines have been prepared. The barrier to inversion is usually in the range of 30-3S kcal/mol so that enantiomerically pure phosphines are stable at room temperature but racemize by inversion at elevated tempeiatuies. Asymmetrically substituted tetracoordinate phosphorus compounds such as phosphonium salts and phosphine oxides are also chiral. Scheme 2.1 includes some examples of chiral phosphorus compounds. 

Phosphonium salts containing a benzyl group may be converted into ylides by the use of only moderately strong bases such as sodium ethoxide. The preparation of benzyli-dene derivatives of aldehydes and ketones is therefore easily done. The procedure below is for the preparation of a substituted butadiene, which in turn is ideally suited for use in the Diels-Alder reaction (see Chapter 8, Section I). 

Bromo-j3-nitrostyrene and triphenylphosphine in dry benzene gave the phosphonium bromide (47). Using methanol as the solvent, the rearranged product (48) was formed, possibly via an azirine intermediate. Substituted -bromo-/3-nitrostyrenes yield the phosphoranes (49) and a phosphonium salt. When the aryl group is electron-donating, the reaction follows a different course to form the styrene (50) by initial attack of the phosphine on halogen. 

A number of keto-carotenoids have been prepared from the bis-phosphonium salt (130) and substituted Cjs-aldehydes, the keto-functions... 

One catalyst that has been found amenable to alkyl systems is CH3P(r-Bu)2 or the corresponding phosphonium salt.228 A range of substituted alkyl bromides were coupled with arylboronic acids. 

Recently, water-soluble phosphonium salts were synthesized and their Wittig reactions with substituted benzaldehydes were carried out in aqueous sodium hydroxide solution (Eq. 8.114).309... 

Feist-Benary cyclo-condensation of (2,4-dioxobutylidene)-phosphoranes with a-chloroacetone gave rise to substituted furfuryl phosphonium salts, which underwent subsequent Wittig reactions to afford alkenylfurans in good yields as can be seen below <06JOC8045>. 

JOC6503>, and new pyridazino-psoralens 15 were prepared via a furan ring expansion reaction <05T4805>. The reaction of 3-acetylcoumarins with alloxan followed by NH2NH2 easily produced 3-(2-oxo-2//-chromen-3-yl)-6//,8//-pyrimido[4,5-c]pyridazine-5,7-diones <05JHC1223>. Furano- and pyrano[2,3-c]pyridazines 17 and 18a,b as well as substituted quinolines were conveniently prepared from pyridazinone 16 and vinyl- and allyltriphenyl-phosphonium salts <05HAC56>. 

There are numerous similarities between ammonia and phosphine, but the latter is a much weaker base (see Chapter 9). In fact, phosphonium salts are stabilized by large anions that are also the conjugates of strong acids. Accordingly, the most common phosphonium salts are the iodides, bromides, tetrafluoroborates, and so forth. Phosphine and substituted phosphines are good Lewis bases toward soft Lewis acids, and many coordination compounds of this type are known. 

The ylide obtained from (methyl)triphenylphosphonium bromide reacts with morpholine derivatives 597 to give phosphonium salts 598 which upon treatment with -butyllithium are converted to new ylides 599. In a reaction with aldehydes, ylides 599 form iV-(l,3-disubstituted allyl)-morpholines 602 (Scheme 94) <1996AQ138>. Another less common nucleophile that can be used for substitution of the benzotriazolyl moiety in Af-(a-aminoalkyl)benzotriazoles is an adduct of iV-benzylthiazolium salt to an aldehyde which reacts with compounds 597 to produce adducts 600. Under the reaction conditions, refluxing in acetonitrile, salts 600 decompose to liberate aminoketones 601 <1996H(42)273>. 

Another substituted derivative of BINAP was used by Lemaire et al. [109]. The ammonium salt catalysts (7 and 8, Fig. 41.10) were prepared in situ from the bro-mohydrates and [Ru( /3-2-methylallyl)2(/72-COD)], and immobilized in several ionic liquids. By comparative studies of the hydrogenation of ethyl acetoacetate, the best results were obtained with imidazolium- and pyridinium-containing ionic liquids. No significant ee was observed with the phosphonium salt. This observation was attributed to problems of solubility and to the ability of complexation for the phosphonium ion. From the anionic side, use of the [BF4] anion appeared superior compared to [PF6] and [(CF3S02)2N]A... 

Phosphoniosilylotion. This combination reacts with acyclic or cyclic enones to give phosphonium salts, formed by addition of P(C6H,)3 to the p-position of the enone and silylation of the carbonyl group. The products can be converted into p-substituted enones by deprotonation (BuLi), a Wittig reaction, and hydrolysis. 

Allylphosphonium salts are synthesized by substitution of allyl halides with PPh3. The use of allyl alcohol, allyl acetate, or nitropropene with a palladium catalyst has also been reported.19 It is shown in this study that the organophosphorous compounds can be obtained by a palladium-catalyzed addition to an allene. A notable aspect of this method is that it can control the stereochemistry of the phosphonium salt, and that (Z)-allylphosphonium salts have been obtained in pure form for the first time. 

It is interesting that the reaction of triphenylphosphine with a 1,2-allenyl ketone leads to the formation of a vinyl phosphonium salt 449, which upon protection of the carbonyl group would accept nucleophilic attack followed by elimination in the presence of Et3N to afford y-nudeophile substituted- ,/j-unsaturated enones 451 [197]. 

The first catalysts utilized in phase transfer processes were quaternary onium salts. In particular, benzyltriethylammonium chloride was favored by Makosza (7 ) whereas Starks utilized the more thermally stable phosphonium salts (6,8). In either case, the catalytic process worked in the same way the ammonium or phosphonium cation exchanged for the cation associated with the nucleophilic reagent salt. The new reagent, Q+Nu , dissolved in the organic phase and effected substitution. 

Other Onium Salt Catalysts. We have examined several quaternary ammonium and phosphonium salts in this process. And while they vary in their effectiveness, most seem to have at least some activity. In the case of symmetrical onium salts, substituents having four or more carbon atoms are preferred (Table III). This likely originates from a more favorable partitioning into the organic phase as the size of the substitutents increase. Herriott has reported that there is a... 

The formation of the heterocycle 1 from the xylylene-bis-phosphonium salt 2 and PCI3 proceeds via a detectable intermediate 3 in a cascade of condensation reactions that is terminated by spontaneous heterolysis of the last remaining P-Cl bond in a cyclic bis-ylide-substituted chlorophosphine formed (Scheme 1) [15]. The reaction scheme is applicable to an arsenic analogue of 1 [15] and to bis-phosphonio-benzophospholides with different triaryl-, aryl-alkyl- and aryl-vinyl-phosphonio groups [16, 18, 19], but failed for trialkylphosphonio-substituted cations here, insufficient acidity prohibited obviously quantitative deprotonation of the phosphonium salts, and only mixtures of products with unreacted starting materials were obtained [19]. The cations were isolated as chloride or bromide salts, but conversion of the anions by complexation with Lewis-acids or metathesis was easily feasible [16, 18, 19] and even salts with organometallic anions ([Co(CO)4] , [CpM(CO)3] (M=Mo, W) were accessible [20]. 

Thianthrene radical ion(l+) perchlorate was employed to effect one-electron oxidation of Cu(TPP) (TPP, tetraphenylporphyrinate) to [Cu (Tpp )]+[sbcy (82JA6791). It was also used to dehydrogenate thio-xanthene (44)(R = H), forming perchlorate 43 or, in the presence of an electron-rich aromatic, the 9-Ar-substituted-thioxanthene 44 (R = Ar) (80MI4 82MI4) or, in the presence of a phosphine, phosphonium salts 44 (R = P-"R (81MI7). 

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