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Symmetric substrates

The possible ambiguities that may arise in ring syntheses based upon nueleophilic reaetions with a-halo ketones are also exemplified by the reactions with a-lithioaldimines leading to pyrrole formation, as shown in Scheme 73a 73TL3517). A simitar problem could well arise in the related carbazole synthesis indicated in Scheme 73b if a less symmetrical substrate was employed 81TL1475). [Pg.130]

Note that the same holds true for [ 1, j] sigmatropic reactions of symmetrical substrates... [Pg.1491]

Kinetic resolution reactions on C2-symmetric substrates have important applications. Desymmetrization is just one example of such a kinetic resolution reaction. Enzymatic desymmetrization is outlined in Scheme 8-1.5,6... [Pg.453]

The new spiroannelation method gives, by use of both the tin and silicon chemistry, ready access to [4.4], [4.5], [5.5], [4.6], and [5.6] spirocyclic systems as well as five-, six-, and seven-membered rings possessing a quaternary center. An in situ oxidation, or protection of an initially formed crude secondary alcohol increases the ease of isolation of the product and leads to improved overall yields. Furthermore, for symmetrical substrates, this chemodifferentiates two oxygen functionalities at... [Pg.250]

The enzymatic reaction mechanism was determined by incubating a-carotene 6, a non-symmetric substrate of the enzyme, under a 02 atmosphere in H2 0 followed by isolation and characterization of derivatives of the cleavage product 2 (6). Accordingly, the enzyme cleaving the central double bond of 1 was found to be a non-heme iron monooxygenase (P-carotene 15,15 -monooxygenase) and not dioxygenase as termed earlier (Fig. 3). From the chemical point of view this enzymatic reaction is very unusual for various reasons (i) the reaction... [Pg.33]

A more complicated picture arises with substrates containing more than one stereocentre which could be subject to redox stereoinversion of the type described in the previous examples. With two carbinol stereocentres in a symmetrical substrate there exist a maximum of five stereoisomers (the R,R and S,S enantiomers and meso isomer of the diol and two enantiomers of the intermediate a-hydroxyketone) for the dehydrogenase enzyme(s) to discriminate and transform irreversibly to a single enantiomer. Of course for 1,2-diols the intermediate j -hydroxyketone may be spontaneously equilibrating through an... [Pg.66]

Base removes a proton from adjacent to a carbonyl group. We can use a general to represent the base however, we could use hydroxide, since that is released upon dissolving sodium carbonate in water. It does not matter which a-position we choose they are actually all equivalent in this symmetrical substrate. The nucleophilic attack of the enolate anion onto the second carbonyl is followed by base-initiated dehydration, so that a favourable conjugated ketone is the product. As you can see, the size of the ring systems is automatically defined by the reaction. [Pg.658]

The application of immobilized heterobimetallic cobalt-rhodium in nanoparticles has also been reported. In the presence of water, CO, and amine, internal acetylenes 119 were converted to 3,4-disubstituted furan-2(5H)-ones 120 and 121 in high yields, in which an amine was necessary for the formation of furanone and a higher CO pressure was required for good yield (Equation (8)). It is important to notice that the catalyst has been easily recovered without loss of activity or formation of hydrogenated side-products. The reaction proceeded in good yield for the symmetric substrates (entries 1 and 2) while it always gave two regioisomers for asymmetric alkyne substrates (entries 3-8). The isomer ratio was dependent on the steric and electronic nature of the substituents. [Pg.525]

It was not until 1948 that Ogston popularized the concept that by binding with substrates at three points, enzymes were capable of asymmetric attack upon symmetric substrates.d In other words, an enzyme could synthesize citrate with the carbon atoms from acetyl-CoA occupying one of the two -CH2COOH groups surrounding the prochiral center. Later, the complete stereochemistry of the... [Pg.954]

The crucial difference between nonenzymatic and enzymatic reactions is that the former generally take place in a homogeneous solution, whereas the latter occur on the surface of a protein that is asymmetric. Because of this, an asymmetric enzyme is able to confer asymmetry on the reactions of symmetric substrates. For example, although the two hydrogen atoms in CH2RR are equivalent in simple chemical reactions, the equivalence may be lost when the compound binds to the asymmetric active site of an enzyme.3 The attachment to the enzyme by R and R in structure 8.7 causes the two hydrogen atoms to be exposed to... [Pg.461]

Fig. 34 Racemic but enantiomorphous structures of [7]H on Cu(lll) [88], Opposite tilt angles with respect to a highly symmetric substrate direction of heterochiral M - P double rows create left-tilted X domains (a) and right-tilted p domains (b). The sign of the tilt angle is determined by the relative position of the M - P enantiomers in a heterochiral pair... Fig. 34 Racemic but enantiomorphous structures of [7]H on Cu(lll) [88], Opposite tilt angles with respect to a highly symmetric substrate direction of heterochiral M - P double rows create left-tilted X domains (a) and right-tilted p domains (b). The sign of the tilt angle is determined by the relative position of the M - P enantiomers in a heterochiral pair...
Instead of starting with racemic starting material it is also possible to use symmetric substrates [25]. The hydrolase selectively catalyses the hydrolysis of just one of the two esters, amides or nitriles, generating an enantiopure product in 100% yield (Scheme 6.7). No recycling is necessary, nor need catalysts be combined, as in the dynamic kinetic resolutions, and no follow-up steps are required, as in the kinetic resolutions plus inversion sequences. Consequently this approach is popular in organic synthesis. Moreover, symmetric diols, diamines and (activated) diacids can be converted selectively into chiral mono-esters and mono-amides if the reaction is performed in dry organic solvents. This application of the reversed hydrolysis reaction expands the scope of this approach even further [22, 24, 27]. [Pg.271]

Most of the poly functional substrates belonging to this group of compounds have two (or more) active hydrogen atoms located on different positions of the molecule. Thus, in the case of symmetrical substrate with two identical reactive XH groups 109, the Mannich bases 110-115 (Rg. 42) arc obtained by reaction of the. substrate with formaldehyde and amine in the molar ratio 123. [Pg.174]

By the choice of a symmetrical substrate or a substrate containing only one activated position selective fluorinations of aromatic compounds have been achieved (Table 17). [Pg.44]

Stereoselectivity in the hydroboration of asymmetric substrates is described in Section D.2.5.2.1.1. The organoborane products shown there are usually oxidized to the corresponding alcohols. In a similar manner to the symmetric substrates above, cyclic, asymmetric and functionalized alkenes, e.g., a-pinene24 and cholesterol2S, are attacked by borane and more selectively by substituted boranes from the less hindered side16-20-21 26-29. [Pg.24]

The addition of a small symmetrical molecule, such as bromine, to a symmetrical substrate, such as ethene, is the simplest type of two step addition reaction. We will look at this reaction in some detail in order to highlight the factors involved. [Pg.222]

We will use the addition of hydrogen bromide to ethene as an example of the addition of an unsymmetrical molecule to a symmetrical substrate. [Pg.230]

So far we have looked largely at substrates which are flat achiral objects that have chiral centres introduced by means of a reagent. Desymmetrisations are slightly different. Molecules which are desymmetrised tend to be of a meso type. That is, they are achiral because they have a mirror plane and the sides of the molecule contain left and right handed portions 219. This is in contrast to the C2 axis present in many catalysts such as the TADDOLate 218. Desymmetrisations are powerful because there may be several chiral centres embedded in an achiral molecule which suddenly become much more useful in the newly formed chiral molecule. There are a large variety of symmetrical substrates that have been enantioselectively desymmetrised48 and we look at a few of the more important classes. [Pg.558]

Symmetrical diketones react normally with either one (equation 12) ° or two (equation 13) equivalents of the Reformatsky reagent. There are no reports of selective reaction at a single carbonyl of an un-symmetrical substrate, although this has been accomplished by selective acetal protection (Scheme 5). ... [Pg.283]

Conditions for the reductive desulfurization of 3,6-bis(methylthio)pyridazine (108), (Scheme 70) with Raney nickel have been developed as part of a synthetic approach to 4- or 4,5-disubstituted pyridazines based on Diels-Alder reactions of 3,6-bismethylthio-l,2,4,5-tetrazine. Selective oxidation of (108) can give the monosulfoxide, bis(sulfoxide), and bis(sulfone) depending on the conditions used, and the bis(sulfone) was susceptible to nucleophilic displacement of one sulfonyl group. These studies were limited to the symmetrical substrate (108) <88JOCi4i5>. [Pg.54]

Certain half-reactions imply a regiospecificity which is often not warranted when applied to particular synthon skeletons. All s =l half-reactions are of course regiospecific as involving only one carbon and most s =3 half-reactions are clearly directive owing to functional asymmetry, but s =2 half-reactions with symmetrical substrate functionality are not. These are essentially those with substrate /-lists of 11, 11, or 22, t.e., 12,52,12,12. 2 and with minimum /-lists. A major synthetic problem of regiospecificity is the A2 reaction when either CH adjacent to ketone may act as enolate, and the A3 reaction, also with tauto-merically equivalent a- and y-carbons, has the same problem. In many such functionally symmetrical cases it is skeletal asymmetry which offers regiospecificity, and this is simply expressed in the different or-values of the two carbons competing for the construction. [Pg.87]

The reactions of symmetrical M = M compounds with symmetrical substrates are expected to yield products in which the metal atoms are in equivalent environments. Whenever an exception is found, low energy pathways will readily interconvert the two ends of the dinuclear compound. [Pg.406]

The general reactions proposed herein for M = M compounds with symmetrical substrates are not exhaustive but merely pertinent to some recent experimental observations. The reaction schemes involving unsymmetrical substrates and heteronuclear M-M multiple bonded compounds are virtually unlimited, all of which indicates the growth potential of this area of transition metal chemistry. [Pg.406]

This type of behavior means that the enzyme can bind a symmetrical substrate in an unsymmetrical binding site. In Section 7.6, we mentioned that this possibility exists, and here we have an example of it. The enzyme forms an unsymmetrical three-point attachment to the citrate molecule (Figure 19.6). The reaction proceeds by removal of a water molecule from the citrate to produce 5-aconitate, and then water is added back to the m-aconitate to give isocitrate. [Pg.553]


See other pages where Symmetric substrates is mentioned: [Pg.18]    [Pg.18]    [Pg.285]    [Pg.326]    [Pg.24]    [Pg.350]    [Pg.231]    [Pg.248]    [Pg.1659]    [Pg.1197]    [Pg.580]    [Pg.222]    [Pg.350]    [Pg.473]    [Pg.193]    [Pg.93]    [Pg.234]   


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