Sulfur-stabilized carbocations

A new method for the synthesis of 2-substituted, as well as 2,4- and 2,5-disubstituted, cyclopentanones in 53-93% yield has been reported.81 For example, the Lewis acid catalyzed transformation of l-propanoyl-l-(4-tolylsulfanyl)cyclobutane gave 2-ethyl-2-(4-tolylsulf-anyl)cyclopentanone (1) in 93 % yield. The formation of the cyclopentanone is best explained by a mechanism which involves initial coordination of aluminum trichloride to the carbonyl oxygen, followed by ring expansion to form the sulfur-stabilized carbocation. Finally, migration of the ethyl group to the carbocation center regenerates concomitantly the carbonyl function.81... 

You may protest that these last two species are not carfoo-cations at all but rather sulfonium ions, and you would be right. However, they can be used in place of carbocations as they are electrophilic at carbon so it is useful to think of them as modified carbocations as well as sulfonium ions. Sulfur-stabilized a-cations are easily made from a-chlorosulfides and are useful in alkylation of silyl enol ethers. 

Sulfur-stabilized (3-carbocations (three-membered rings)... 

In many respects the Pummeter reaction can be regarded as the sulfur version of the Polonovski reaction (and vice versa), and by analogy to the Polonovski reaction the central intermediate is a sulfur-stabilized carbocation (thionium ion). Although the existence of this species is only transient, it reacts to give a number of different products, e.g. a-acetoxy sulfides, vinyl sulfides, cationic cyclization products, etc., depending upon the sulfoxide structure and reaction conditions. Other reaction pathways ate specific to the Pummerer reaction as a result of sulfur s ability to expand its valence shell (additive Pum-merer reactions). A moderate degree of asymmetric induction is also observed in certain Pummerer reactions, where optically pure sulfoxides are substrates. 

This reaction probably occnrs not only in red bnt also in white wine. The carbocations are stabilized by reacting with nucleophilic compounds, snch as the sulfur compounds present in very small quantities that are responsible either for off-flavors or characteristic aromas. The sulfur compounds may be inhibited in this way (Figure 6.24) and lose their unpleasant organoleptic characteristics (odor and flavor). 

Elimination of Benzylic Phenyl Thioethers. That C-S bond activation by CuOTf is not limited to substrates that can generate sulfur-stabilized carbocation intermediates is illustrated by a C-C connective synthesis of trans-stilbene (eq 56). The elimination of thiophenol under mild conditions is favored by benzylic stabilization of a carbocation intermediate or an E2 transition state with substantial carbocationic character. 

Ionizations of furfuryl alcohols in trifluoroacetic acid solutions lead to the formation of fliranoxonium ions. These resonance-stabilized carbocations have been used in (4 + 3)-cycloaddition reactions with 1,3-dienes. Erker and coworkers have found that 2,5-dimethylthiophene (182) undergoes a novel trimerization reaction in solution of hexanes and CF3S03H. The tetracyclic product (183) is formed in high yield and its structure was confirmed by X-ray crystallography. A mechanism is proposed for the conversion, invoking C(2) protonated 2,5-dimethylthiophene as the initial eleetrophilic species. Subsequent intermediates are sulfur-stabilized carbocations and dications. 

The results of ab initio calculations provide evidence that Me2NC(S)-[14+] is stabilized by resonance electron donation from the a-thioamide group (A, Scheme 12) and by covalent bridging of sulfur to the benzylic carbon (B, Scheme 12).96 Direct resonance stabilization of the carbocation will increase the barrier to the nucleophile addition reaction, because of the requirement for the relatively large fractional loss of the stabilizing resonance interaction (A, Scheme 12) at the transition state for nucleophile addition to a-substituted benzyl carbocations.8,13,28 91-93 If the solvent adds exclusively to an open carbocation that is the minor species in a mixture of open and closed ions, then... 

Since these methoxylated and acetoxylated sulfides have an acetal structure, it is expected that Lewis acid catalyzed demethoxylation should generate a carbocation intermediate which is stabilized by the neighboring sulfur atom. In fact, nucleophilic substitution with arenes has been successfully achieved as shown in Scheme 6.7 [43], This procedure is useful for the preparation of trifluoroethyl aromatics. As already mentioned, generation of carbocations bearing an a-trifluoromethyl group is difficult due to the strong electron-withdrawing effect. Therefore, this carbon-carbon bond formation reaction is remarkable from both mechanistic and synthetic aspects. 

CF3 compounds like (23) in which the sulfur substituent stabilizes the carbocation, /3-allylation and -cyanation is possible. Scheme 10. Normally, / -substitution of CF3 compounds is problematic because of competing elimination [34]. 

Tertiary alcohols dehydrate most readily, primary alcohols least readily, and, unsurprisingly, secondary alcohols are intermediate. This relates to the relative stability of the intermediate carbocation. The temperature and concentration of the acid depends upon the type of alcohol. A primary alcohol, such as ethanol, requires concentrated acid and a very high temperature (180 degrees Celsius), while a tertiary alcohol, such as t-butyl alcohol, requires 20 percent sulfuric acid at 85 to 90 degrees Celsius. The process follows an El mechanism and produces the thermodyncimically more stable product. 

The results so far suggest that stabilization of the intermediate carbocation by an adjacent heteroatom, aromatic ring or by steric factors stimulates fluorination of a CLH bond by sulfur tetrafluoride. 

The effect of monofluorination on alkene or aromatic reactivity toward electrophiles is more difficult to predict Although a-fluonne stabilizes a carbocation relative to hydrogen, its opposing inductive effect makes olefins and aromatics more electron deficient. Fluorine therefore is activating only for electrophilic reactions with very late transition states where its resonance stabilization is maximized The faster rate of addition of trifluoroacetic acid and sulfuric acid to 2-fluoropropene vs propene is an example [775,116], but cases of such enhanced fluoroalkene reactivity in solution are quite rare [127] By contrast, there are many examples where the ortho-para-dueeting fluorine substituent is also activating in electrophilic aromatic substitutions [128]... 

Advantage has been taken of the ready accessibility of eleven para-substituted trityl and 9-phenylxanthyl cations, radicals, and carbanions in a study of the quantitative relationship between their stabilities under similar conditions.2 Hammett-type correlations have also been demonstrated for each series. Heats and free energies of deprotonation and the first and second oxidation potentials of the resulting carbanions were compared. The first and second reduction potentials and the p/CR values of the cations in aqueous sulfuric acid were compared, as were calorimetric heats of hydride transfer from cyanoborohydride ion. For radicals, consistent results were obtained for bond dissociation energies derived, alternatively, from the carbocation and its reduction potential or from the carbanion and its oxidation potential. 

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