A-Hydroxycarboxylate

Besides simple alkyl-substituted sulfoxides, (a-chloroalkyl)sulfoxides have been used as reagents for diastereoselective addition reactions. Thus, a synthesis of enantiomerically pure 2-hydroxy carboxylates is based on the addition of (-)-l-[(l-chlorobutyl)sulfinyl]-4-methyl-benzene (10) to aldehydes433. The sulfoxide, optically pure with respect to the sulfoxide chirality but a mixture of diastereomers with respect to the a-sulfinyl carbon, can be readily deprotonated at — 55 °C. Subsequent addition to aldehydes afforded a mixture of the diastereomers 11A and 11B. Although the diastereoselectivity of the addition reaction is very low, the diastereomers are easily separated by flash chromatography. Thermal elimination of the sulfinyl group in refluxing xylene cleanly afforded the vinyl chlorides 12 A/12B in high chemical yield as a mixture of E- and Z-isomers. After ozonolysis in ethanol, followed by reductive workup, enantiomerically pure ethyl a-hydroxycarboxylates were obtained. 

No or little side reactions either with the unprotected hydroxy group present in the phenylamines, or with the unprotected hydroxyl group present in the carboxylic acids are observed. The catalytic amidation of unprotected a-hydroxycarboxylic acids also proceeds well under similar conditions. 

Dochnahl M, Fu GC (2009) Catalytic asymmetric cycloaddition of ketenes and nitroso compounds enantioselective synthesis of a-hydroxycarboxylic acid derivatives. Angew Chem Int Ed 48 2391-2393... 

Acidification with trichloracetic acid catalyses oxidation , the fractional increase in the rate coefficient per mole of acid added, viz. Ak/ko)/[sicid], being of the order of two. Strong catalysis by alkali metal acetates has been observed for several oxidations, e.g. of m-cyclohexane-l,2-diol °, formic acid , methyl mannoside and galactoside and several a-hydroxycarboxylic acids °. 

It is important that the synthesis should be carried out as quickly as possible, particularly the washing with alkali at 0°, since the latter tends to convert the product into cyctopentane-a-hydroxycarboxylic acid. 

A concerted mechanism is also possible for a-hydroxycarboxylic acids, and these compounds readily undergo oxidative decarboxylation to ketones.281... 

Rhodococcus erythropolis NCIMB 11540 has been employed as biocatalyst for the conversion of (R)- or (.S )-cyanohydrins to the corresponding (R)- or (S)-a-hydroxycarboxylic acids with an optical purity of up to >99% enatiomeric excess (ee) [27-29] the chiral cyanohydrins can separately be produced using hydroxynitrile lyase from Hevea braziliensis or from Prunus anygdalis [30]. Using the combined NHase-amidase enzyme system of the Rhodococcus erythropolis NCIMB 11 540, the chiral cyanohydrins were first hydrolyzed to the... 

Measured at pH 7.0, which may not necessarily be the potential-limiting pH. dDonor groups 2 hydroxamate and 1 a-hydroxycarboxylate. 

Donor groups 1 hydroxamate, 1 catecholate, and 1 a-hydroxycarboxylate. Donor groups 1 catecholate and 2 a-hydroxycarboxylate. 

Besides the known activity of HRuX(PPh3)3 complexes where X is a carboxylate (/, p. 85), other complexes with X an a-hydroxycarboxylate and related bridged dimers [HRu(PPh3)3]2X have been found to effect alkene hydrogenation (124). 

The application of RCM to dihydropyran synthesis includes a route to 2,2-disubstituted derivatives from a-hydroxycarboxylic acids. In a one-pot reaction, the hydroxy esters undergo sequential O-allylation, a Wittig rearrangement and a second O-allylation to form allyl homoallyl ethers 8. A single RCM then yields the 3,6-dihydro-2//-pyran 9. The process is readily adapted not only to variably substituted dihydropyrans but also to 2-dihydrofuranyl and 2-tetrahydrooxepinyl derivatives and to spirocycles e.g. 10 through a double RCM (Scheme 4) <00JCS(P1)2916>. 

Rates of ligand exchange depend quite strongly on the coordina-tive environment of the metal center. The water exchange rate of Fe(H2O)5(OH)is almost three orders of magnitude higher than that of Fe(H20)g+, and follows a dissociative, rather than an associative exchange mechanism (20). Fe(1120)5(OH)has also been shown to form inner-sphere complexes with phenols (27), catechols (28), and a-hydroxycarboxylic acids (29) much more quickly than Fe(H20) +. The mechanism for complex formation with phenolate anion (A-) is shown below (27) ... 

Block copolymers of (R,S)-(3-butyrolactone and eCL have been synthesized by combining the anionic ROP of the first monomer with the coordinative ROP of the second one (Scheme 15) [71]. The first step consisted of the synthesis of hydroxy-terminated atactic P(3BL by anionic polymerization initiated by the alkali-metal salt of a hydroxycarboxylic acid complexed with a crown ether. The hydroxyl end group of P(3BL could then be reacted with AlEt3 to form a macroinitiator for the eCL ROP. 

Carbon dioxide itself can accept e. during radiolysis of water, giving rise to the carbon dioxide anion-radical. This anion-radical can add to carboradicals. Thus, aliphatic alcohols react with the radiolytically generated hydroxyl radicals, rupturing their C—H bonds RCHjOH + OH HjO + RCH OH. These radicals accept the radiolytically generated COj" forming a-hydroxycarboxylic acids RCHjOH + CO2 RCH(OH)COO (Morkovnik and Okhlobystin 1979). 

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