9.9: Alquinos a Aldehídos y Cetonas: Hidroboración-Oxidación
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
The hydroboration-oxidation reaction is a two-step process. It begins with the hydroboration step, which involves a concerted syn addition of BH3 across the carbon–carbon triple bond to form an alkenylborane. The concerted nature of the reaction also accounts for the anti-Markovnikov regiochemistry, where the BH2 group adds to the less substituted carbon and H to the more substituted carbon of the triple bond.
Three successive hydroboration reactions convert an alkene into a trialkenylborane intermediate. The second part of the sequence is oxidation, where the trialkenylborane is treated with alkaline hydrogen peroxide to form an enol. The enol eventually converts into a stable carbonyl product via keto-enol tautomerism.
Hydroboration of Alkynes with Disubstituted Boranes
Unlike alkenes, hydroboration of alkynes does not stop at the first addition of BH3. This is because alkynes have two π bonds, each capable of reacting with BH3. The first addition forms an organoborane, which is an alkene derivative that can react further with another equivalent of BH3.
Terminal alkynes being less hindered than internal alkynes are more susceptible to a second BH3 addition. With internal alkynes, the addition of BH3 stops after the first stage and proceeds in a direction to give the trialkenylborane.
Nevertheless, hydroboration of terminal alkynes can be stopped at the first step by using bulky disubstituted boranes (R2BH) such as disiamylborane and 9-BBN instead of BH3.
The first addition of the bulky reagent forms a sterically hindered alkenylborane that resists any further additions and helps in the efficient conversion of alkynes to stable carbonyl compounds.