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Substitution reactions bond cleavage

The phosphine oxide (38) is known to undergo nucleophilic substitution reactions with cleavage of either a phosphorus-phenyl bond, or one of the heterocyclic... [Pg.78]

Figure 37.2. Catalysis by the enzyme chymotrypsin of the cleavage of one peptide bond in a protein a proposed mechanism. Histidine and pro-tonated histidine act as general base and acid in two successive nucleophilic substitution reactions (a) cleavage of protein with formation of acyl enzyme and liberation of one protein fragment (6) hydrolysis of acyl enzyme with regeneration of the enzyme and liberation of the other protein fragment. Figure 37.2. Catalysis by the enzyme chymotrypsin of the cleavage of one peptide bond in a protein a proposed mechanism. Histidine and pro-tonated histidine act as general base and acid in two successive nucleophilic substitution reactions (a) cleavage of protein with formation of acyl enzyme and liberation of one protein fragment (6) hydrolysis of acyl enzyme with regeneration of the enzyme and liberation of the other protein fragment.
The hydrogenolyaia of cyclopropane rings (C—C bond cleavage) has been described on p, 105. In syntheses of complex molecules reductive cleavage of alcohols, epoxides, and enol ethers of 5-keto esters are the most important examples, and some selectivity rules will be given. Primary alcohols are converted into tosylates much faster than secondary alcohols. The tosylate group is substituted by hydrogen upon treatment with LiAlH (W. Zorbach, 1961). Epoxides are also easily opened by LiAlH. The hydride ion attacks the less hindered carbon atom of the epoxide (H.B. Henhest, 1956). The reduction of sterically hindered enol ethers of 9-keto esters with lithium in ammonia leads to the a,/S-unsaturated ester and subsequently to the saturated ester in reasonable yields (R.M. Coates, 1970). Tributyltin hydride reduces halides to hydrocarbons stereoselectively in a free-radical chain reaction (L.W. Menapace, 1964) and reacts only slowly with C 0 and C—C double bonds (W.T. Brady, 1970 H.G. Kuivila, 1968). [Pg.114]

Amides are the least reactive caiboxyhc acid deiivative and the only nucleophilic acyl substitution reaction they undeigo is hydrolysis Amides are fanly stable m water but the amide bond is cleaved on heating m the presence of strong acids 01 bases Nomi nally this cleavage produces an amine and a caiboxyhc acid... [Pg.862]

The strength of their carbon-halogen bonds causes aryl halides to react very slowly in reactions in which carbon-halogen bond cleavage is rate determining as m nude ophilic substitution for example Later m this chapter we will see examples of such reactions that do take place at reasonable rates but proceed by mechanisms distinctly dif ferent from the classical S l and 8 2 pathways... [Pg.972]

A number of studies of the acid-catalyzed mechanism of enolization have been done. The case of cyclohexanone is illustrative. The reaction is catalyzed by various carboxylic acids and substituted ammonium ions. The effectiveness of these proton donors as catalysts correlates with their pK values. When plotted according to the Bronsted catalysis law (Section 4.8), the value of the slope a is 0.74. When deuterium or tritium is introduced in the a position, there is a marked decrease in the rate of acid-catalyzed enolization h/ d 5. This kinetic isotope effect indicates that the C—H bond cleavage is part of the rate-determining step. The generally accepted mechanism for acid-catalyzed enolization pictures the rate-determining step as deprotonation of the protonated ketone ... [Pg.426]

Curvature in a Br nsted-type plot is sometimes attributed to a change in transition state structure. This is not a change in mechanism rather it is interpreted as a shift in extent of bond cleavage and bond formation within the same mechanistic pattern. Thus, Ba-Saif et al. ° found curvature in the Br nsted-type plot for the identity reactions in acetyl transfer between substituted phenolates this reaction was shown earlier. They concluded that a change in transition state structure occurs in the series. Jencks et al." caution against this type of conclusion solely on the evidence of curvature, because of the other possible causes. [Pg.354]

Chiral oxazolines developed by Albert I. Meyers and coworkers have been employed as activating groups and/or chiral auxiliaries in nucleophilic addition and substitution reactions that lead to the asymmetric construction of carbon-carbon bonds. For example, metalation of chiral oxazoline 1 followed by alkylation and hydrolysis affords enantioenriched carboxylic acid 2. Enantioenriched dihydronaphthalenes are produced via addition of alkyllithium reagents to 1-naphthyloxazoline 3 followed by alkylation of the resulting anion with an alkyl halide to give 4, which is subjected to reductive cleavage of the oxazoline moiety to yield aldehyde 5. Chiral oxazolines have also found numerous applications as ligands in asymmetric catalysis these applications have been recently reviewed, and are not discussed in this chapter. ... [Pg.237]

Reactions of isoxazole derivatives that take place with the cleavage of the heterocyclic nucleus are as characteristic in this series as the substitution reactions. They are due to the cleavage of the bond... [Pg.397]

The JV-silyl phosphinous amides present some particularities in their reactivity that make these compounds worth commenting on separately. They are stable and can be easily prepared in the usual way by reaction of AT-silyl substituted primary amines or hexamethyldisilazane with halophosphanes [48,49,128,129] or byJV-silylation of the appropriate phosphinous amides [72, 107]. The reductive Ph-P bond cleavage in AT-silyl phosphazenes Ph3P=NSiMe3 by the action of sodium is a peculiar example of preparing Ph2PNHSiMe3 [130]. [Pg.92]

As mentioned in Section II.B.I., ligand substitution at Mo2Co2(/X4-S)(/i3-S)2(CO)4(/ -C5H4Me)2l occurred by way of an adduct at cobalt, with acompensat-ing Co—S bond cleavage (Fig. although for PMc3 reaction did not proceed... [Pg.66]

The aryl-thallium bond is thus apparently capable of displacement either by electrophilic or by suitable nucleophilic reagents. Coupled with its propensity for homolytic cleavage (spontaneous in the case of ArTlIj compounds, and otherwise photochemically induced), ArTlXj compounds should be capable of reacting with a wide variety of reagents under a wide variety of conditions. Since the position of initial aromatic thallation can be controlled to a remarkable degree, the above reactions may be only representative of a remarkably versatile route to aromatic substitution reactions in which organothallium compounds play a unique and indispensable role. [Pg.173]

According to the H-NMR spectra in DMSO - de, benzodiazepine 69 exists as a 4 1 mixture of tautomers A and A. Benzodiazepin-2-one 69 is formed due to the substitution of the hydroxyl group of coiunarin 67 by one of the amino groups of o-phenylenediamine and the C - O bond cleavage in the py-rone ring upon reaction with the second amino group. [Pg.149]

The complete process for synthesizing such species using this approach would entail the acquisition of an appropriate natural silicate or the preparation of an appropriate synthetic silicate and then the conversion of this silicate into the alkyl silicate or organosiloxane by suitable substitution reactions. In terms of bond cleavage, this process could entail no destruction and reformation of framework silicon-oxygen bonds, and, in terms of oxidation number, it would entail no reduction and reoxidation of the silicon. [Pg.240]


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See also in sourсe #XX -- [ Pg.60 , Pg.61 ]

See also in sourсe #XX -- [ Pg.17 , Pg.192 ]

See also in sourсe #XX -- [ Pg.192 ]




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Cleavage reaction

Substitution reactions without metal-ligand bond cleavage

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