Chem. Oct. 24th

Carbocation Stability

  • Key Point: When deciding the carbocation to form, always choose the most stable one.
  • The stability of carbocations increases with the degree of substitution:
    • Tertiary (3°) > Secondary (2°) > Primary (1°) > Methyl (0°)
  • Water acts as a nucleophile, attacking the carbocation to lead to the formation of alcohols.

Reagents: BH₃ and THF

  • BH₃ (Boron Hydride):
    • Structure: Boron is electron-deficient with only 6 valence electrons.
    • Requires stabilization by a solvent, typically THF (tetrahydrofuran).
  • THF:
    • Acts as a solvent to stabilize BH₃ by weakly binding to boron using lone pairs, though it's not a true covalent bond.

Mechanism of Reaction with BH₃

  • When BH₃ interacts with an alkene:
    • The hydrogen (H) is less electronegative than carbon, leading to a polar bond.
    • A partial positive charge (δ⁺) develops on boron, and a partial negative charge (δ⁻) on hydrogen.
    • Electron-rich species (like a pi bond) will attack the electron-poor boron.
  • As the alkene forms a bond with boron, a positive charge (carbocation) forms on the adjacent carbon.
  • The hydrogen from BH₃ helps stabilize the carbocation, leading to the more substituted alkene (Markovnikov addition).

Regioselectivity and Stereoselectivity with BH₃ = H₂O

  • First step: BH₃ adds across the double bond to form the more substituted carbocation.
  • Second step: The reaction converts BH₂ into OH when water is introduced.
  • Result: Hydroboration-oxidation results in the OH being located at the least substituted carbon (due to anti-Markovnikov addition).

Stereochemistry of Reactions

  • The reaction mechanism with BH₃ and H₂O is stereoselective, producing only syn addition of H and OH on the same face of the double bond.
  • Important Detail: During hydrogenation (like with H₂ and a metal catalyst), both hydrogens will add to the same side (syn addition).
  • If considering more complex reactions:
    • Reacting with a compound like H₃O⁺ would yield OH on the more substituted carbon instead (Markovnikov addition).

Stability and Hydrogenation Process

  • In the presence of a metal catalyst (like platinum or palladium), H₂ will be added across the double bond, transforming it into an alkane.
  • Notable Point: This reaction is very efficient and requires the proper metal catalyst to work at normal pressures.
  • Hydrogenation will generally cause the two hydrogens to add on the same side, leading to a syn product.

Bromination of Alkenes

  • In the lab:
    • Alkene reacts with Br₂ (brown-red), leading to the rapid consumption of the brown color, indicating reaction.
    • The outcome is formation of an anti product due to the mechanism of bromine addition:
    • The first bromine attaches to the alkene, forming a cyclic bromonium ion.
    • The second bromine attacks from the opposite side, resulting in an anti addition (trans stereochemistry between bromines).
    • This is explained by the need for bromide to attack the less hindered carbon, leading to anti orientation.
  • Notable products are usually a pair of enantiomers due to this anti addition mechanism.

Electrophilic Addition and Stereochemistry

  • Key Mechanism:
    • If an alkene approaches bromine, the electrons will polarize, enabling the alkene to attack the more positive site.
  • Stability of the generated carbocation governs the product outcome:
    • Important to note that only anti addition occurs with bromine due to the back-attack mechanism on the carbocation.

Summary of Key Takeaways

  • Hydration via BH₃ results in syn addition, with OH on the least substituted carbon, contradicting typical Markovnikov behavior seen with H⁃X (like H₃O⁺).
  • Alkene reactivity with Br₂ will yield anti addition products due to formation of a cyclic bromonium ion leading to backside attack by bromide (Br⁻).
  • The presence of a metal catalyst and sufficient reactants is required for effective hydrogenation and reduction of alkenes.
  • Observing the structure and connectivity during transformations will yield insights into resulting stereochemistry and regioselectivity across various electrophilic additions.