Water scheme

Sandstrom et al. (65) evaluated the Kj value for 4,5-dimethyl-A-4-thiazoline-2-thione (46) in water (Scheme 19) K-j= 10. A-4-Thiazoline-2-thiones are less basic in the first excited state (61) than in the ground state, so application of Forster s cycle suggests that the thione form is even more favored in the first excited state. Huckel molecular orbital (HMO) calculations suggest that electronic effects due to substitution in... 

Figure 9.4 (a) Basic pure MU water scheme CF/BX/RO (b) very pure MU water scheme UF/RO/MB (c) very pure, membrane only, MU water scheme UF/RO/EDI (d) mobile condensate polishing scheme bag filter SAC(H)/MB. 

The simple cyclopropylmethoxycarbenechromium complex 142 reacts with alkynes to afford cyclopentenones 143 and 144 via the cyclopentadiene intermediate 145, which is hydrogenated with the aid of the chromium(O) residue and water (Scheme 31) [100-103]. Formation of 145 can be regarded as... 

Copper-complexes prepared with other type of N-chelating ligands have been also prepared and evaluated as catalysts for the Diels-Alder reaction. Eng-berts et al. [103] studied enantioselective Diels-Alder reaction of 3-phenyl-l-(2-pyridyl)-2-propen-l-one with cyclopentadiene in water (Scheme 39). By using coordinating chiral, commercially available a-amino-adds and their derivatives with copper salts as catalysts, they obtained the desired product with yields generally exceeding 90%. With L-abrine (72 in Scheme 39) as chiral moiety, an enantiomeric excess of 74% could be achieved. Moreover, the catalyst solution was reused with no loss of enantioselectivity. 

It was previously observed that with a catalytic amount of FeCls, benzylic alcohols were rapidly converted to dimeric ethers by eliminating water (Scheme 14). In the presence of an alkyne this ether is polarized by FeCls and generates an incipient benzylic carbocation. The nucleophilic attack of the alkyne moiety onto the resulting benzyl carbocation generated a stable alkenyl cation, which suffer the nucleophilic attack of water (generated in the process and/or from the hydrated... 

The allylation of aldehydes can be carried out using stannous chloride and catalytic cupric chloride or copper in aqueous media." In-situ probing provides indirect (NMR, CV) and direct (MS) evidence for the copper(I)-catalyzed formation of an allyltrihalostannane intermediate in very high concentration in water (Scheme 8.6). Hydrophilic palladium complex also efficiently catalyzes the allylation of carbonyl compounds with allyl chlorides or allyl alcohols with SnCl2 under aqueous-organic... 

Phosphonic acid analogues 8.2 and 8.3 of both KDN and N-acetylneuraminic acid have been synthesized using the indium-mediated coupling of the lower carbohydrates with dimethyl 3-bromopropenyl-2-phosphonate (8.4) in water (Scheme 8.9).124... 

The same coordination is used to account for the observed anti preference in the allylation of (t-hydroxybutanal with allyl bromide/indium in water (Scheme 8.16). The intermediate leads to the anti product. In support of the intramolecular chelation model, it is found that if the hydroxy group is converted to the corresponding benzyl or t-butyldimethylsilyl ether, the reaction is not stereoselective at all and gives nearly equal amounts of syn and anti products. 

Compounds 260a-c have been studied with respect to their vulnerability to nucleophilic attack. Reactions were carried out between these compounds and pyridine, pyridine/water, DBU, and DBU/water (Scheme 25). The products formed were found to depend on the nucleophilicity and/or the basicity of the reagents used < 1998PS( 132)183>. 

In boron enolate-mediated aldol reactions, stoichiometric amounts of boron reagents are necessary. However, it has been reported that only a catalytic amount of a boron source is sufficient for boron enolate-mediated aldol reactions in water (Scheme 65).302 It should be noted that even water-sensitive boron enolates can be successfully employed in water. 

A paper concerning the synthesis of miharamycin analogues modified in the sugar moiety demonstrated the hydrolysis of a nitrile upon treatment with silica gel in the presence of water (Scheme 37).174 The cyanide 197 resulting from the opening of epoxide... 

Several microwave-assisted procedures have been described for soluble polymer-supported syntheses. Polyethylene glycol) (PEG)-supported aryl bromides have been shown to undergo rapid palladium(0)-catalyzed Suzuki couplings with aryl boronic acids in water (Scheme 12.16) [63], The reaction proceeded without organic cosolvent... 

A value of kjkp = 17 000 has been determined for partitioning of the acetophenone oxocarbenium ion [12+] in water.15,16 It is not possible to estimate an equilibrium constant for the addition of water to [12+], because of the instability of the hemiketal product of this reaction. However, kinetic and thermodynamic parameters have been determined for the reaction of [12+] with methanol to form protonated acetophenone dimethyl ketal [12]-OMeH+ and for loss of a proton to form a-methoxystyrene [13] in water (Scheme 10).15,16 Substitution of these rate and equilibrium constants into equation (3) gives values of AMeoH = 6.5 kcal mol-1 and Ap = 13.8 kcal mol-1 for the intrinsic... 

Subsequently, we focused on iron(III) complexes. Reaction of the ferric precursor [NEt4]2[Cl3FeOFeCl3] (93) with Hbpza (3a) or Hbdmpza (3b) yielded two equivalents of [NEt4][Fe(bpza)Cl3] (3a) and [NEt4][Fe(bdmpza)Cl3] (3b) by the loss of one equivalent of water (Scheme 10). The structure of 4b is depicted in Fig. 9. 

The structural integrity of enzymes in aqueous solution is often compromised by the addition of small quantities of water-miscible organic solvents. However, there are numerous examples, particularly using extremophiles, where enzymes have been successfully employed in organic solvent-aqueous mixtures.A good example is the savinase-catalysed kinetic resolution of an activated racemic lactam precursor to abacavir in 1 1 THF/water (Scheme 1.39). The organic solvent is beneficial as it retards the rate of the unselective background hydrolysis. 

These observations led to the catalytic application of well-defined ruthenium alkyUdenes, some of them freely soluble and sufficiently stable in water (Scheme 7.9) although their stability was found somewhat less in aqueous solutions than in methanol [21,27,28], With these catalysts a real living ROMP of water-soluble monomers could be achieved, i.e. addition of a suitable monomer to a final solution of a quantitative reaction resulted in further polymerization activity of the catalyst [28], This is particularly important in the preparation of block copolymers. 

The trifluoromethyl group is found in a wide variety of pharmaceuticals. Besides its effect on the electron density, its high lipophilicity improves transport characteristics in vivo and facilitates lower dosage rates. F for F isotopic exchange reaction has been used to synthesize [l- F]l,l-difluoro-2,2-dichloroethyl-arylethers. The substitution proceeds in good to excellent yields (> 85 %) and is strongly dependent on the reaction conditions. Substitution occurs even at room temperature in DMSO or in acetonitrile containing up to 20% of water (Scheme 61) [247]. 

In recent studies, Jamison and coworkers reported the formation of tetrahydro-pyran via cascade epoxide-opening reactions in water (Scheme 9) [96]. In this study, polytetrahydropyran precursor, such as 53, was synthesized from the epoxidation of polyalkene 52. 

De Mello et al. have constructed a so-called pSYNTAS (miniaturized synthesis and total analysis system). The system was used to perform an Ugi-type reaction to form several a-aminoacetamides from amines, isocyanates and formaldehyde in the presence of water (Scheme 25) [56-58]. The reported system consists of a glass/silicon nanoreactor [59] in connection to a TOF-MS for the real-time online analysis of the reaction stream. Reactions were conducted in the 600 nl volume chip under continuous flow of 20-2 pl/min flow rate. Reduced flow rates resulted in increased outputs. The analyzed outlet flow showed high yields of the desired products with small quantities of starting materials and intermediates (no exact yields were reported). 

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