Phase-transfer catalysis PTC

PTC is a common approach used to accelerate a biphasic reaction by ensuring a ready supply of necessary reagent to the phase in which the reaction occurs [90, 91]. Each reactant is dissolved in the appropriate solvent, which may be immiscible and then a phase transfer catalyst is added to promote the transport of one reactant into the other phase. 

In the first step, deprotonation of the methylene-containing substrate generally takes place at the interface of two phases (liquid-liquid or solid-liquid). 

Subsequent ion exchange of the metal cation with the quaternary ammonium ion catalyst provides a lipophilic ion pair (step 2), which either reacts with the requisite alkyl electrophile at the interface (step 3) or is partitioned into the electrophile-containing organic phase, whereupon alkylation occurs and the catalyst is reconstituted. Enantioselective PTC has found apphcation in a vast number of chemical transformations, including alkylations, conjugate additions, aldol reactions, oxidations, reductions, and C-X bond formations.  

Since the mid-1990s, the phase transfer preparation of enantioenriched a-amino acids has received a great deal of attention, and several types of 

The chemical reaction in an organic solvent involving a reagent which is only very slightly soluble in that solvent (but which is freely soluble in an immiscible aqueous phase) will necessarily be slow. However, if the concentration of this reagent in the organic phase 

Either a chemical reaction or an anion mass transfer (which is dependent on the catalyst concentration and on the interfacial area) can be rate determining, depending on their relative rates. A recent review by Naik and Doraiswamy covers the subject comprehensively [11]. 

Carbanions can be generated and alkylated in a two-phase liquid-liquid system using concentrated aqueous sodium or potassium hydroxide as the base. Makosza has shown that deprotonation occurs at the interface, Fig. 5.10 [12]. 

---

Fluonnated allylic ethers are prepared under phase-transfer catalysis (PTC) in the presence of tetrabutylammonium hydrogen sulfate (TBAH) fJ] (equation 2)... 

It is important to make the distinction between the multiphasic catalysis concept and transfer-assisted organometallic reactions or phase-transfer catalysis (PTC). In this latter approach, a catalytic amount of quaternary ammonium salt [Q] [X] is present in an aqueous phase. The catalyst s lipophilic cation [Q] transports the reactant s anion [Y] to the organic phase, as an ion-pair, and the chemical reaction occurs in the organic phase of the two-phase organic/aqueous mixture [2]. 

Interests in the phase transfer catalysis (PTC) have grown steadily for the past several years [68-70]. The use of PTC has recently received industrial importance in cases where the alternative use of polar aprotic solvents would be prohibitively expensive [71-74]. Thus, the potential application of the phase transfer catalyzed aromatic nucleophilic displacement reactions between phenoxide or thiophenoxide and activated systems has... 

Various synthetic routes to isocyanides have been reported since their identification over 100 years ago.8 Until now, the useful synthetic procedures all required a dehydration reaction8-11 Although the carbylamine reaction involving the dichlorocarbene intermediate is one of the early methods,8 it had not been preparatively useful until the innovation of phase-transfer catalysis (PTC).4 5... 

Phase transfer catalysis (PTC) refers to the transfer of ions or organic molecules between two liquid phases (usually water/organic) or a liquid and a solid phase using a catalyst as a transport shuttle. The most common system encountered is water/organic, hence the catalyst must have an appropriate hydrophilic/lipophilic balance to enable it to have compatibility with both phases. The most useful catalysts for these systems are quaternary ammonium salts. Commonly used catalysts for solid-liquid systems are crown ethers and poly glycol ethers. Starks (Figure 4.5) developed the mode of action of PTC in the 1970s. In its most simple... 

Although the use of phase-transfer catalysis (PTC) for manufacturing esters has the merits of a mild reaction condition and a relatively low cost [1], PTC has its limitations, such as the low reactivity of carboxylic ion by liquid-liquid PTC [2], a slow reaction rate by solid-liquid PTC, and the difflculty of reusing the catalyst by both techniques. 

Phase transfer catalysis (PTC) has been utilized in organic synthesis to perform reactions in organic solvents when some of reactants are present in the aqueous phase (e.g., the substitution reaction involving alkylchlorides RCl),... 

Homogenous (Homo) Heterogeneous (Het) Biocatalytic (Bio) Phase Transfer Catalysis (PTC). 

In the mid-1960s a series of papers by Makosza and Serafinowa (1965, 1966) appeared under the common title Reactions of Organic Anions , in which the catalytic alkylation of phenylacetonitrile and its derivatives carried out in the presence of concentrated NaOH and the catalyst triethylbenzylammonium chloride (TEBA) was described. This was the beginning of phase-transfer catalysis (PTC), and since then thousands of papers haven been published on the subject. 

Higher selectivity, easier processing, use of inexpensive solvents, use of cheaper chemicals, and ease of heat removal have been realized through phase-transfer catalysis (PTC). It appears that no catalytic method has made such an impact as PTC on the manufacture of fine chemicals (Sharma, 1996). Many times we benefit by deliberately converting a single-phase reaction to a two-phase reaction. Consider catalysis by. sodium methoxide in a dry organic. solvent. This can invariably be made cheaper and safer by using a two-pha.se. system with a PT catalyst. 

Compounds 242 when treated with trimethylsulfonium iodide under phase-transfer catalysis (PTC) conditions ( -Bu4XI, dichloromethane, 50% NaOH) provide mixtures of the corresponding 2-oxiranylvinyl benzotriazoles 243 and 18-83% yields of heteropentalenes 244. The ratio of these two main products is highly dependent on the R substituent (Scheme 29) <2004ARK(ii)109>. 

Alkylation of dianhydrohexitols under phase-transfer catalysis (PTC) conditions... 

Solvent-free Solid-Liquid Phase-transfer Catalysis (PTC)... 

Loupy and Soufiaoui described a comparative study of the reactivity of diphenylnitri-limine 200 with several dipolarophiles under microwave irradiation in the absence of solvent using a solid mineral support or phase-transfer catalysis (PTC) conditions (Scheme 9.62) [30b]. The results showed that the best yields of adducts were achieved upon impregnating KF-alumina with a mixture of the hydrazynoyl chloride 199 and the dipolarophile followed by irradiation of the mixture in a focused oven. Reaction of this mixture under solid-liquid PTC conditions with KF-Aliquat under microwaves afforded lower yields of cycloadducts, perhaps owing to the partial decomposition of Aliquat at the reaction temperature (140 °C). In all cases, worse yields were obtained by classical heating under comparable reaction conditions (time and temperature). 

We have exploited this base catalysis of the oxygen exchange process to effect oxygen lability in the less electrophilic carbonyl sites of neutral metal carbonyl species. Because [MCOOH] intermediates are readily decarboxylated in the presence of excess hydroxide ion, in order to observe oxygen exchange processes in neutral metal carbonyl complexes it was convenient to carry out these reactions in a biphasic system employing phase transfer catalysis () (16, 17. 18). Under conditions (eq. 7) the... 

Concept Phase transfer catalysis (PTC)111 is now a convenient and useful tool in chemistry, especially in preparative organic chemistry. In general, compounds (reactants) located in different phases of a reaction mixture such as water and benzene sluggishly react each other even by harsh stirring the mixture because the reactants can not easily contact together. Phase transfer catalysts transfer between different phases, become highly active species, and catalytically medi-... 

The cocatalytic effects of pinacol in the phase transfer catalysis (PTC) of dihalocarbene additions to alkenes were noted by Dehmlow and co-workers who showed that pinacol accelerates the PTC deprotonation of substrates up to pKa 27.7 Dehmlow also studied the effects of various crown ethers as phase transfer catalysts in the addition of dibromocarbene to allylic bromides.8 In Dehmlow s study, elevated temperature (40°C) and dibenzo-18-crown-6 did not give the highest ratio of addition/substitution to allyl bromide. However, the submitters use of pinacol,... 

Uniquely interesting, complex and useful activities and phenomena occur at interfaces one need only to look at the interfaces between the land, the atmosphere, and the sea to find this truth. The same truth occurs in chemical interfaces, although sometimes it is the lack of activity that draws our attention. In many chemical situations where two species cannot collide and therefore cannot react because they are separated by an interface, the lack of activity has been overcome by use of the technique of PHASE TRANSFER CATALYSIS (PTC), which not only allows reaction to occur, but often to occur in very selective ways. 

The first examples of the application of phase-transfer catalysis (PTC) were described by Jarrousse in 1951 (1), but it was not until 1965 that Makosza developed many fundamental aspects of this technology (2,3). Starks characterized the mechanism and coined a name for it (4,5), whilst Brandstrom studied the use of stoichiometric amounts of quaternary ammonium salts in aprotic solvents, "ion-pair extraction" (6). In the meantime Pedersen and Lehn discovered crown-ethers (7-9) and cryptands (10,11), respectively. 

Figure 11.5. Representative example of the mechanistic pathway of phase transfer catalysis (PTC). (Z, Z — functional group M = metal Q = chiral catalyst R = alkyl or aryl reagent X = halogen).

To facilitate accesses to suitably functionalized sialic acid derivatives and complex sialyloligosaccharides for other usehil neoglycoconjugates, phase transfer catalysis (PTC) has been exploited extensively [for reviews see 42]. This process provided a wide range of carbohydrate derivatives under essentially clean Sn2 transformations. In the case of acetochloroneuraminic acid 1, the PTC reactions always provided inverted a-sialic acid derivatives [43]. para-Formylphenyl sialoside 7 [44], together with many other sialoside derivatives such as 8-10 [43], including thioacetate 12 [45] and azide 14 [46], were thus obtained (Scheme 1). Aldehyde 7 and similar glycosides are of particular interest since they could be directly conjugated to protein by reductive amina-tion after suitable deprotection [44]. 

Supercritical fluids are benign alternatives to conventional organic solvents that may offer improvements in reaction rate, product selectivity, and product separation. We reported the first use of SCFs for phase-transfer catalysis (PTC), where these benign alternatives also offer greatly improved transport, product separation, catalyst recycle, and facile solvent removal (26-29). 

---