Acyl moiety

Fig. 3. The stmcture of the nodulation (Nod) factors of i bium meliloti 2011 (44), where is 2 or 3, R is —H or—COCH, and R is C 2 as shown, C gT, or ie, a fatty acid chain having from 1 to 3 double bonds. The A/-acetyl glucosamine residues and an acyl moiety, R, are present ia all...

A number of examples of monoacylated diols produced by enzymatic hydrolysis of prochiral carboxylates are presented in Table 3. PLE-catalyzed conversions of acycHc diesters strongly depend on the stmcture of the substituent and are usually poor for alkyl derivatives. Lipases are much less sensitive to the stmcture of the side chain the yields and selectivity of the hydrolysis of both alkyl (26) and aryl (24) derivatives are similar. The enzyme selectivity depends not only on the stmcture of the alcohol, but also on the nature of the acyl moiety (48). 

Both saturated (50) and unsaturated derivatives (51) are easily accepted by lipases and esterases. Lipase P from Amano resolves azide (52) or naphthyl (53) derivatives with good yields and excellent selectivity. PPL-catalyzed resolution of glycidyl esters (54) is of great synthetic utiUty because it provides an alternative to the Sharpless epoxidation route for the synthesis of P-blockers. The optical purity of glycidyl esters strongly depends on the stmcture of the acyl moiety the hydrolysis of propyl and butyl derivatives of epoxy alcohols results ia esters with ee > 95% (30). 

Two more examples ia Table 5 iaclude the hydrolysis of esters of trans-alcohols that proceed with high efficiency practically regardless of the nature of the substituents (72) and resolution of P-hydroxynitriles with Upase from Pseudomonas sp. In the latter case the enantioselectivity of the hydrolysis was improved by iatroduciag sulfur iato the acyl moiety (73). 

You should have identified that the acyl moiety, phenylacetic add, is the second product arising from the hydrolysis of penicillin G. This could be recovered from the reaction mixture and reused as a precursor for penicillin G production. In practice, an integrated process is used. We can represent this in the following way ... 

The yeast pyruvate decarboxylase is rather specific with respect to the acyl moiety that is added to the aldehyde. Only a few 2-oxo acids can be used as acyl donors besides pyruvic-acid39. For example, treatment of benzaldehyde with 2-oxobutanoic acid and 2-oxopentanoic acid, respectively, and prewashed Saccharomyces cerevisiae gave the corresponding (/ )-acyloin derivatives in 15 25% yield with an enantiomeric excess >95%. 

Primarily hydrolyses esters with short acyl moiety, such as acetylcholine (ACh). It is the major ChE in human blood, muscle and brain cells. AChE mRNA is 20-fold more abundant than BChE mRNA. 

Primarily hydrolyses esters with longer aliphatic (compared to AChE) or aromatic acyl moiety, such as butyrylcholine (BCh) and benzoylcholine (BzCh). BChE is the primary circulating ChE. It is threefold more abundant than AChE in human blood and is found in liver, lungs, muscles, brain and heart. 

Esterases, proteases, and some lipases are used in stereoselective hydrolysis of esters bearing a chiral or a prochiral acyl moiety. The substrates are racemic esters and prochiral or meso-diesters. Pig liver esterase (PLE) is the most useful enzyme for this type of reaction, especially for the desymmetrization of prochiral or meso substrates. 

Penicillin G acylase (PGA, EC 3.5.1.11, penicillin G amidase) catalyzes the hydrolysis of the phenylacetyl side chain of penicillin to give 6-aminopenicillanic acid. PGA accepts only phenylacetyl and structurally similar groups (phenoxyacetyl, 4-pyridylacetyl) in the acyl moiety of the substrates, whereas a wide range of structures are tolerated in the amine part [100]. A representative selection of amide substrates, which have been hydrolyzed in a highly selective fashion, is depicted in Figure 6.36. 

A stereochemical point of considerable interest concerns the position of entry of L with respect to the newly formed acyl moiety. This has been investigated for RMn(CO)5 and CpMo(CO)3R. 

Another aspect of stereochemistry of the CO insertion which has received attention concerns the actual process of formation of the acyl moiety from the coordinated CO and R. Three possible pathways may be envisaged. First, the alkyl moves from the metal onto an adjacent CO. This is known as the alkyl migration mechanism. Second, a coordinated CO moves to insert into the M—R bond—a CO insertion mechanism. Third, both CO and R move in a cooperative manner. These three pathways are represented schematically in Eq. (46). 

G. V. Bloembcrg, E. Kamst, M. Hartevcid, K. M. G. M. van der Drift, J. Haverkamp, J, E. Thomas-Oates, B. J. J. Lugtenberg, and H. P. Spaink. A central domain of Rhizobium NodE protein mediates host specificity by determining the hydropho-bicity of fatty acyl moieties of nodulation factors. Mol. Microbiol. I6 123 (1995). 

If the acyl moiety is sensitive to acid and base the imidazolide method for synthesis of (acylmethylidene)phosphoranes is the method of choice, as shown by the following example, which represents a step on the way to the antibiotic methynolide ... 

Migration of the imidazolylcarbonyl group in addition to N-C migration of the acyl moiety was observed upon irradiation of l-(dehydroabietoyl)imidazole and l-(13 -de-isopropyl-10 -e/ -dehydroabietoyl)imidazole.[3]... 

Yonekura, L, Tsuzuki, W, and Nagao, A, 2006. Acyl moieties modulate the effects of phospholipids on beta-carotene uptake by Caco-2 cells. Lipids 41, 629-636. 

Cholesterol esters are produced by transferring an acyl moiety from acyl-CoA or from phosphatidylcholine onto the cholesterol hydroxyl group. The latter process is catalyzed by phosphatidylcholine cholesterol acyltransferase ... 

The polymerase is stereospecific. It accepts only the D-(-)-stereoisomer which is generally formed by the NADPH-linked reductase. With respect to chain length of the activated fatty acids the specificity of the polymerase varies in different organisms. It links not only C4 3-acyl moieties but also C5 compounds when forming the polyester molecule [26]. It also polymerizes 3-hy-droxy-, 4-hydroxy-, and 5-hydroxyalkanoates from C3 to C5 monomers, but not C6 or higher (e.g., in R. eutropha) [27-31]. In pseudomonads, in contrast, it links C6 to C14 3-hydroxyalkanoyl-CoA [32]. 

TAGs are abbreviated as Tx where x is relative to the Equivalent Carbon Number (ECN) that corresponds to the number of carbon atoms of all the acyl moieties of the TAG. 

An additional example is the observed moderate acceleration in the cleavage of particular phenyl esters in the presence of a cyclodextrin. In such cases, the bound ester is attacked by an hydroxyl group on the cyclodextrin to yield a new ester. There was found to be a significant enhancement of phenol release from meta-substituted phenyl acetate on interaction with cyclodextrin (relative to other esters which do not fit the cavity so well) (Van Etten, Clowes, Sebastian Bender, 1967). During the reaction, the acyl moiety transfers to an hydroxyl group on the... 

In a,jS-unsaturated stannyl esters the acyl moiety is displaced by mercury(II) salts without affecting carbon-carbon double bonds, as shown in reaction 71322. 

Ester saponifaction was a favoured reaction for this type of study, because the hydrophobicity of the acyl moiety could easily be controlled by increasing the length of an n-alkyl group, and saponification of p-nitrophenyl n-alkanoates could be followed with very dilute substrate. Substrate concentration is an important factor, because provided that it is kept low it is reasonable to assume that the micelle structure is relatively unperturbed. 

Figure 11.3 Fischer projection of a triacylglycerol. The fatty acyl moieties are represented by R, R" and R " positioned at sw-1, sn-2 and sn-3 respectively.

Methanolysis can occur via inter- or intramolecular nucleophilic attacks by MeOH at the carbon atom of a Pd-acyl moiety and produces an ester end group and a Pd - H+ species. Again, the hydride may deprotonate with formation of less active Pd(0) and dimeric species (Fig. 3) [47,57]. 

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