Electrophilic Additions to Alkynes. Vinyl Cations

Electrophiles react with alkynes in much the same way as with alkenes. Alkynes are typically much less reactive toward electrophiles than alkenes (see Chapter 7, Problem 14), however, and the initial product from addition to the triple bond usually undergoes further electrophilic addition. 

The first step in the addition of an electrophile such as HBr to an alkyne involves protonation and subsequent formation of an intermediate vinyl cation. Where does propyne protonate Compare energies of 1-methylvinyl and 2-methylvinyl cations. Which is more stable Why Measure CC bond distance in the more stable cation. Does the cation incorporate a full triple bond (as in propyne) or a double bond (as in propene). Examine atomic charges and electrostatic potential maps to locate the positive charge in the two cations. Is the more stable ion the one in which the charge is better delocalized Use the charges together with information about the ions geometry to draw Lewis structures (or a series of Lewis structures) for 1-methylvinyl and 2-methylvinyl cations. 

Is the location of positive charge in the more stable cation also where the lowest-unoccupied molecular orbital (LUMO) is most concentrated Rationalize what you observe. Does attack by a nucleophile (bromide) lead to the Markovnikov or anti Markovnikov product  

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The three basic mechanisms that have been considered to be involved in electrophilic additions to alkynes are shown below. The first involves a discrete vinyl cation. In general, it can lead to either of the two stereoisomeric addition products. The second mechanism is a termolecular process which would be expected to lead to stereospecific anti addition. The... 

The exact behavior and mechanism of electrophilic additions to alkynes is clearly strongly dependent upon the reaction conditions. In a highly polar and strongly acidic but weakly nucleophilic solvent such as trifluoroacetic acid, addition via a vinyl cation intermediate is favored whereas in less polar, more nucleophilic solvents such as acetic acid, a different mechanism prevails. 

For reviews of electrophilic addition to alkynes, including much evidence, see Rappoport React. Interned. (Plenum) 1983, 3, 427-615, pp. 428-440 Stang Rappoport Hanack Subramanian Vinyl Cations, Academic Press New York. 1979. pp. 24-151 Stang Prog. Phys. Org. Chem. 1973, 10. 205-325 Modena Toncllato Adv. Phys. Org. Chem. 1971, 9, 185-280. pp. 187-231 Richey Richey, in Olah Schleycr Carbonium Ions, vol. 2 Wiley New York, 1970. pp. 906-922. 

The relative stability of vinyl and saturated cations in solution can in principle be evaluated by following three approaches (a) from the competitive formation of vinyl and saturated cations in electrophilic addition to allenes (b) from the relative rates of electrophilic addition to alkynes and alkenes (c) from the relative rates of solvolysis of vinyl and saturated derivatives. 

Alkynes undergo the same set of reactions as alkenes but are slightly less reactive because the intermediates involved are less stable. For the Ade2 process, the vinyl cation intermediate formed is less stable than the alkyl carbocations formed when electrophiles attack alkenes. Addition to the vinyl cation produces a mixture of syn and anti addition. Stabilizing the vinyl cation by bridging is less favorable since the bridged ion is more strained and may have some antiaromatic character. 

The basic mechanisms that are considered to be involved in electrophilic additions to alkynes are outlined below. The first involves a discrete vinyl cation. In general, this reaction will lead to a mixture of the two stereoisomeric addition products. Mechanisms B and C depict bridged intermediates formed without (B) or with (C) participation of a second electrophilic molecule. Mechanisms B and C should lead to anti addition. Mechanism D is a termolecular process that would be expected to be a stereospecific anti addition. Mechanisms A and B are of the Adg2 type, whereas C and D are classified as Ad S. Each of these mechanisms may involve a prior complex formation between the alkyne and an electrophile. 

For a discussion of vinyl cations and electrophilic additions to alkynes, see Stang, P. J. Rappoport, Z. Hanack, M. Subramanian, L. R. Vinyl Cations Academic Press New York, 1979. 

Alkynes, although not as prevalent as alkenes, have a number of important uses in synthesis. In general, alkynes are somewhat less reactive than alkenes toward many electrophiles. A major reason for this difference in reactivity is the substantially higher energy of the vinyl cation intermediate that is formed by an electrophilic attack on an alkyne. It is estimated that vinyl cations are about lOkcal/mol less stable than an alkyl cation with similar substitution. The observed differences in rate of addition in direct comparisons between alkenes and alkynes depend upon the specific electrophile and the reaction conditions.111 112 Table 4.4 summarizes some illustrative rate comparisons. A more complete discussion of the mechanistic aspects of addition to alkynes can be found in Section 6.5 of Part A. 

The mercuric ion-catalyzed hydration of alkynes probably proceeds in a similar manner to the oxymercuration of alkenes (see Section 5.1). Electrophilic addition of Hg to the triple bond leads to a vinylic cation, which is trapped by water to give an vinylic organomercury intermediate. Unlike the alkene oxymercuration, which requires reductive removal of the mercury by NaBH4, the vinylic mercury intermediate is cleaved under the acidic reaction conditions to give the enol, which tautomerizes to the ketone. Hydration of terminal alkynes follows the Mai kovnikov rule to furnish methyl ketones. ° ... 

Evidence from a variety of sources however indicates that alkenyl cations (also called vinylic cations) are much less stable than simple alkyl cations and their involve ment m these additions has been questioned Eor example although electrophilic addi tion of hydrogen halides to alkynes occurs more slowly than the corresponding additions... 

Alkynes react with bromine via an electrophilic addition mechanism. A bridged bromonium ion intermediate has been postulated for alkyl-substituted acetylenes, while vinyl cations are suggested for aryl-substituted examples.119 1-Phenylpropyne gives mainly the anti addition product in acetic acid, but some of the syn isomer is formed.120 The proportion of dibromide formed and stereoselectivity are enhanced when lithium bromide is added to the reaction mixture. 

An alkyne is less reactive than an alkene. A vinyl cation is less able to accommodate a positive charge, as the hyperconjugation is less effective in stabilizing the positive charge on a vinyl cation than on an alkyl cation. The vinyl cation is more stable with positive charge on the more substituted carbon. Electrophilic addition reactions allow the conversion of alkenes and alkynes into a variety of other functional groups. 

Prior to this report, the addition of bromine to alkynes in acetic acid was suggested to occur via an electrophilic process (although not explicitly involving vinyl cations as intermediates) by Robertson et al. (1950). The reaction rate was found to obey mixed second and third-order kinetics and to be enhanced by electron-supplying substituents. It was also noted that strong electron-withdrawing residues bonded to the triple bond may switch the reaction pattern towards a nucleophilic... 

As showm in Figure 8.3, the mechanism of the mercury ID-catalyzed alkyne hydration reaction is analogous to the oxymercuration reaction of alkenes (Section 7.4). Electrophilic addition of mercury(Il) ion to the alkyne gives a vinylic cation, which reacts with water and loses a proton to yield a mercury-containing enol intermediate. In contrast with alkene oxymercuration, however, no treatment with NaBl-14 is necessary to remove the mercury. The acidic reaction conditions alone are sufficient to effect replacement of mercury by hydrogen. 

They react with terminal alkynes by electrophilic addition of the empty p-orbital to the unsubstituted end of the triple bond 83. The intermediate would then be the more substituted vinyl cation 84. It is easier to draw this mechanism with R2BH than with the full structure for 9-BBN. The intermediate 84 is not fully formed before hydride transfer begins so that the reaction is semi-concerted and the transition state is something like 86. The result is a regioselective and stereospecific cis hydroboration of the triple bond to give the A-vinyl borane 85. The intermediate 84 is quite like the radical intermediate in hydrostannylation but the difference is that hydrogen transfer is intramolecular and stereospecific in hydroboration. 

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