Oxonium ions reaction

We can extend the general principles of electrophilic addition to acid catalyzed hydration In the first step of the mechanism shown m Figure 6 9 proton transfer to 2 methylpropene forms tert butyl cation This is followed m step 2 by reaction of the car bocation with a molecule of water acting as a nucleophile The aUcyloxomum ion formed m this step is simply the conjugate acid of tert butyl alcohol Deprotonation of the alkyl oxonium ion m step 3 yields the alcohol and regenerates the acid catalyst... 

Once formed the tetrahedral intermediate can revert to starting materials by merely reversing the reactions that formed it or it can continue onward to products In the sec ond stage of ester hydrolysis the tetrahedral intermediate dissociates to an alcohol and a carboxylic acid In step 4 of Figure 20 4 protonation of the tetrahedral intermediate at Its alkoxy oxygen gives a new oxonium ion which loses a molecule of alcohol m step 5 Along with the alcohol the protonated form of the carboxylic acid arises by dissocia tion of the tetrahedral intermediate Its deprotonation m step 6 completes the process... 

It is possible to balance all of these thermodynamic, kinetic, and mechanistic considerations and to prepare well-defined PTHF. Living oxonium ion polymerizations, ie, polymerizations that are free from transfer and termination reactions, are possible. PTHF of any desired molecular weight and with controlled end groups can be prepared. 

A protonic acid derived from a suitable or desired anion would seem to be an ideal initiator, especially if the desired end product is a poly(tetramethylene oxide) glycol. There are, however, a number of drawbacks. The protonated THF, ie, the secondary oxonium ion, is less reactive than the propagating tertiary oxonium ion. This results in a slow initiation process. Also, in the case of several of the readily available acids, eg, CF SO H, FSO H, HCIO4, and H2SO4, there is an ion—ester equiUbrium with the counterion, which further reduces the concentration of the much more reactive ionic species. The reaction is illustrated for CF SO counterion as follows ... 

The protonated azirine system has also been utilized for the synthesis of heterocyclic compounds (67JA44S6). Thus, treatment of (199) with anhydrous perchloric acid and acetone or acetonitrile gave the oxazolinium perchlorate (207) and the imidazolinium perchlorate (209), respectively. The mechanism of these reactions involves 1,3-bond cleavage of the protonated azirine and reaction with the carbonyl group (or nitrile) to produce a resonance-stabilized carbonium-oxonium ion (or carbonium-nitrilium ion), followed by attack of the nitrogen unshared pair jf electrons to complete the cyclization. 

Entry 4 shows that reaction of a secondary 2-octyl system with the moderately good nucleophile acetate ion occurs wifii complete inversion. The results cited in entry 5 serve to illustrate the importance of solvation of ion-pair intermediates in reactions of secondary substrates. The data show fiiat partial racemization occurs in aqueous dioxane but that an added nucleophile (azide ion) results in complete inversion, both in the product resulting from reaction with azide ion and in the alcohol resulting from reaction with water. The alcohol of retained configuration is attributed to an intermediate oxonium ion resulting from reaction of the ion pair with the dioxane solvent. This would react until water to give product of retained configuratioiL When azide ion is present, dioxane does not efiTectively conqiete for tiie ion-p intermediate, and all of the alcohol arises from tiie inversion mechanism. ... 

When the reaction is performed in dioxane solution, an o onium ion is formed from the solvent and the chlorosulfite ester. The oxonium ion then undergoes substitution by chloride. l vo inversioRs are involved so that tiie result is overall retention. ... 

It follows that the heat of solution of the oxonium ion in water is 380kJ mol" , intermediate between the values calculated for Na+ (405kJmor ) and K+ (325kJmol" ). Reactions involving proton transfer will be considered in more detail in Section 3.5. 

Nucleophilic addition of an alcohol to the carbonyl group initially yields a hydroxy ether called a hemiacetal, analogous to the gem diol formed by addition of water. HcmiacetaJs are formed reversibly, with the equilibrium normally favoring the carbonyl compound. In the presence of acid, however, a further reaction occurs. Protonation of the -OH group, followed by an El-like loss of water, leads to an oxonium ion, R2C=OR+, which undergoes a second nucleophilic addition of alcohol to yield the acetal. The mechanism is shown in Figure 19.12. 

The hydroxylation reaction, whose stereochemical course is controlled by the strong inherent preference for the formation of a cis-fused 5,5 ring system, creates a molecule which would appear to be well suited for an intramolecular etherification reaction to give ring E of ginkgolide B (1). Indeed, when a solution of 11 in methylene chloride is exposed to camphorsulfonic acid (CSA), a smooth cycli-zation reaction takes place to give intermediate 10 in an overall yield of 75% from 12. The action of CSA on 11 produces a transient oxonium ion at C-12 which is intercepted intramolecularly by the proximal hydroxyl group at C 4. 

Cations which are covalently attached to the allyl anion part by a cr-bond and have sufficient Lewis acid properties offer the broadest versatility and highest levels of stereocontrol, since the C—C bond-forming step can occur in a pericyclic process9 accompanied by allylic inversion. It is reasonable to assume the prior assembly of both reaction partners in an open-chain complex, in which usually the (F )-oxonium ion, avoiding allylic 1,3-strain10, is predominant. 

Oxidation of either alkyl or aryl sulphoxides to sulphones in 65-90% yields may be accomplished by treatment with a nitronium salt15. In the case of aryl sulphoxides no nitration is observed (which is in contrast to the results of nitric acid oxidation). The reaction was shown to proceed through intermediate nitratosulphonium and nitritosulph-oxonium ions, as depicted in equation (7), which were studied by nmr spectroscopy. 

At present, this rule fails only when functional neighboring substituents, capable of anchimeric assistance and in a convenient position with respect to the developing positive charge, can compete with bromine in the charge stabilization of the cationic intermediate (ref. 15). For example, the reaction of some unsaturated alcohols (ref. 16) goes through five- or six-membered cyclic oxonium ions, rather than through bromonium ions. 

The synthesis of different substituted finans by cyclization of 4-pentynones using potassium tert-butoxide in DMF was reported <96TL3387>. Dihydrofuran 32 can be prepared by a destannylative acylation of l-[(2-methoxyethoxy)methoxy]-2-(phenylsulfonyl)-2-(tributylstannyl)-cyclopropane. Treatment of 32 with BFj-EtjO yields 3-acyUurans via an intramolecular Prins-type reaction of the resulting oxonium ion intermediate <96TL4585>. 

The use of iodotrimethylsilane for this purpose provides an effective alternative to known methods. Thus the reaction of primary and secondary methyl ethers with iodotrimethylsilane in chloroform or acetonitrile at 25—60° for 2—64 hours affords the corresponding trimethylsilyl ethers in high yield. The alcohols may be liberated from the trimethylsilyl ethers by methanolysis. The mechanism of the ether cleavage is presumed to involve initial formation of a trimethylsilyl oxonium ion which is converted to the silyl ether by nucleophilic attack of iodide at the methyl group. tert-Butyl, trityl, and benzyl ethers of primary and secondary alcohols are rapidly converted to trimethylsilyl ethers by the action of iodotrimethylsilane, probably via heterolysis of silyl oxonium ion intermediates. The cleavage of aryl methyl ethers to aryl trimethylsilyl ethers may also be effected more slowly by reaction with iodotrimethylsilane at 25—50° in chloroform or sulfolane for 12-125 hours, with iodotrimethylsilane at 100—110° in the absence of solvent, " and with iodotrimethylsilane generated in situ from iodine and trimcthylphenylsilane at 100°. ... 

The boron trifluoride-alkyl thiol reagent combination also operates on the basis of nucleophilic attack on an oxonium ion generated by reaction of the ether with boron trifluoride.90... 

Trimethylsilyl iodide (TMSI) cleaves methyl ethers in a period of a few hours at room temperature.89 Benzyl and f-butyl systems are cleaved very rapidly, whereas secondary systems require longer times. The reaction presumably proceeds via an initially formed silyl oxonium ion. 

These reactions presumably proceed by catalytic cycles in which the carbonyl component is silylated. The silyl ether can then act as a nucleophile, and an oxonium ion is generated by elimination of a disilyl ether. The reduction of the oxonium ion regenerates the silyl cation, which can continue the catalytic cycle. 

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