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Addition of Lewis Acids (Electrophilic Reagents)

The proton is not the only electrophilic species that initiates addition reactions to the double bond. Lewis acids like the halogens, boron hydrides and certain transition metal ions are able to bond to the alkene pi-electrons, and the resulting complexes rearrange or are attacked by nucleophiles to give addition products.

The electrophilic character of the halogens is well known. Although fluorine is uncontrollably reactive, chlorine, bromine and to a lesser degree iodine react selectively with the double bond of alkenes. The addition of chlorine and bromine to alkenes, as shown in the following general equation, proceeds by an initial electrophilic attack on the pi-electrons of the double bond. Iodine adds reversibly to double bonds, but the equilibrium does not normally favor the addition product, so it is not a useful preparative method. Dihalo-compounds in which the halogens are juxtaposed in the manner shown are called vicinal, from the Latin vicinalis, meaning neighboring.

R2C=CR2   +   X2  → R2CX-CR2X

Other halogen containing reagents which add to double bonds include hypohalous acids, HOX, and sulfenyl chlorides, RSCl. These reagents are unsymmetrical, so their addition to unsymmetrical double bonds may in principle take place in two ways. In practice, these addition reactions are regioselective, with one of the two possible constitutionally isomeric products being favored. The electrophilic moiety of these reagents is the halogen.

(CH3)2C=CH2   +   HOBr  → (CH3)2COH-CH2Br
(CH3)2C=CH2   +   C6H5SCl  → (CH3)2CCl-CH2SC6H5

The regioselectivity of the above reactions may be explained by the same mechanism we used to rationalize the Markovnikov rule. Thus, bonding of an electrophilic species to the double bond of an alkene should result in preferential formation of the more stable (more highly substituted) carbocation, and this intermediate should then combine rapidly with a nucleophilic species to produce the addition product. This is illustrated by the following equation.

Electrophilic Moiety

To apply this mechanism we need to determine the electrophilic moiety in each of the reagents.  By using electronegativity differences we can dissect common addition reagents into electrophilic and nucleophilic moieties, as shown on the right. In the case of hypochlorous and hypobromous acids (HOX), these weak Brønsted acids (pKa's ca. 8) do not react as proton donors; and since oxygen is more electronegative than chlorine or bromine, the electrophile will be a halide cation. The nucleophilic species that bonds to the intermediate carbocation is then hydroxide ion, or more likely water (the usual solvent for these reagents), and the products are called halohydrins. Sulfenyl chlorides add in the opposite manner because the electrophile is a sulfur cation, RS(+), whereas the nucleophilic moiety is chloride anion (chlorine is more electronegative than sulfur).

If you understand this mechanism you should be able to write products for the following reactions:


Oxymercuration and Hydroboration

The addition products formed in reactions of alkenes with mercuric acetate and boron hydrides (compounds shown at the bottom of of the reagent list) are normally not isolated, but instead are converted to alcohols by a substitution reaction. These important synthetic transformations are illustrated for 2-methylpropene by the following equations, in which the electrophilic moiety is colored red and the nucleophile blue. The top reaction sequence illustrates the oxymercuration procedure and the bottom is an example of hydroboration.

The light blue vertical line separates the addition reaction on the left from the substitution on the right. The atoms or groups that have been added to the original double bond are colored orange in the final product. In both cases the overall reaction is the addition of water to the double bond, but the regioselectivity is reversed. The oxymercuration reaction gives the product predicted by Markovnikov's rule; hydroboration on the other hand gives the "anti-Markovnikov" product. Complementary reactions such as these are important because they allow us to direct a molecular transformation whichever way is desired.

Mercury and boron are removed from the organic substrate in the second step of oxymercuration and hydroboration respectively. These reactions are seldom discussed in detail; however, it is worth noting that the mercury moiety is reduced to metallic mercury by borohydride (probably by way of radical intermediates), and boron is oxidized to borate by the alkaline peroxide. Addition of hydroperoxide anion to the electrophilic borane generates a tetra-coordinate boron peroxide, having the general formula R3B-O-OH(-). This undergoes successive intramolecular shifts of alkyl groups from boron to oxygen, accompanied in each event by additional peroxide addition to electron deficient boron. The retention of configuration of the migrating alkyl group is attributed to the intramolecular nature of the rearrangement.

Since the oxymercuration sequence gives the same hydration product as acid-catalyzed addition of water (see Brønsted acid addition), we might question why this two-step procedure is used at all. The reason lies in the milder reaction conditions used for oxymercuration. The strong acid used for direct hydration may not be tolerated by other functional groups, and in some cases may cause molecular rearrangement (see above).

The addition of borane, BH3, requires additional comment. In pure form this reagent is a dimeric gas B2H6, called diborane, but in ether or THF solution it is dissociated into a solvent coordinated monomer, R2O-BH3. Although diborane itself does not react easily with alkene double bonds, H.C. Brown (Purdue, Nobel Prize 1979) discovered that the solvated monomer adds rapidly under mild conditions. Boron and hydrogen have rather similar electronegativities, with hydrogen being slightly greater, so it is not likely there is significant dipolar character to the B-H bond. Since boron is electron deficient (it does not have a valence shell electron octet) the reagent itself is a Lewis acid and can bond to the pi-electrons of a double bond by displacement of the ether moiety from the solvated monomer. As shown in the following equation, this bonding might generate a dipolar intermediate consisting of a negatively-charged boron and a carbocation. Such a species would not be stable and would rearrange to a neutral product by the shift of a hydride to the carbocation center. Indeed, this hydride shift is believed to occur concurrently with the initial bonding to boron, as shown by the transition state drawn below the equation, so the discrete intermediate shown in the equation is not actually formed. Nevertheless, the carbocation stability rule cited above remains a useful way to predict the products from hydroboration reactions. You may correct the top equation by clicking the button on its right. Note that this addition is unique among those we have discussed, in that it is a single-step process. Also, all three hydrogens in borane are potentially reactive, so that the alkyl borane product from the first addition may serve as the hydroboration reagent for two additional alkene molecules.