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21.8: Nucleophilic Addition of H– and R–—A Review

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    28281
  • Addition of a hydride anion (H:-) to an aldehyde or ketone gives an alkoxide anion, which on protonation yields the corresponding alcohol. Aldehydes produce 1º-alcohols and ketones produce 2º-alcohols.

    In metal hydrides reductions the resulting alkoxide salts are insoluble and need to be hydrolyzed (with care) before the alcohol product can be isolated. In the sodium borohydride reduction the methanol solvent system achieves this hydrolysis automatically. In the lithium aluminum hydride reduction water is usually added in a second step. The lithium, sodium, boron and aluminum end up as soluble inorganic salts at the end of either reaction. Note! LiAlH4 and NaBH4 are both capable of reducing aldehydes and ketones to the corresponding alcohol.

    Mechanism

    This mechanism is for a LiAlH4 reduction. The mechanism for a NaBH4 reduction is the same except methanol is the proton source used in the second step.

    1) Nucleopilic attack by the hydride anion

    Fix1.jpg

    2) The alkoxide is protonated

    Fix2.jpg

    Addition of a organometallic reagent to an aldehyde or ketone gives an alkoxide anion, which on protonation yields the corresponding alcohol. Aldehydes produce 2º-alcohols and ketones produce 3º-alcohols.

    Addition to formaldehyde gives 1o alcohols

    File:/C:\Users\Joy\AppData\Local\Temp\msohtmlclip1\01\clip_image020.png

    Addition to aldehydes gives 2o alcohols

    11.jpg

    Addition to ketones gives 3o alcohols

    File:/C:\Users\Joy\AppData\Local\Temp\msohtmlclip1\01\clip_image024.png

    Mechanism

    1) Nucleophilic attack

    File:/C:\Users\Joy\AppData\Local\Temp\msohtmlclip1\01\clip_image032.png

    2) Protonation

    File:/C:\Users\Joy\AppData\Local\Temp\msohtmlclip1\01\clip_image034.png

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