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Fluoride removal of a silyl group: the mechanism, step by step

Fluoride attacks the silicon, which is where it would rather be than anywhere else, and the alcohol is released.

rule-derived2 stepsNot a record of what was observed

The pathway runs in 2 steps. What sits between them is a real structure: it is what the reaction passes through, and on a bad day it is what you isolate instead of the product.

Below is the sequence as it is taught. On the platform it is drawn on whatever structures you supply, with the curly arrows resolved to the actual atoms involved rather than to a general case with R groups on it.

The steps

  1. Fluoride attacks the silicon

    Fluoride goes straight for the silicon. The bond it makes there is the strongest bond silicon forms, and making it is what pulls the group off the oxygen.

    Nucleophilic attack at silicon with displacement of the alkoxide. The silicon-fluorine bond is stronger than almost any other bond silicon makes, and that difference is the whole driving force.

  2. The alkoxide takes a proton

    The negatively charged oxygen picks up a hydrogen and the alcohol is back.

    Protonation from the solvent or on work-up.

What this drawing assumes

Read these before you quote the mechanism
  • Drawn as a single attack. Silicon can hold five groups for a moment, and the true path goes through that; the drawing does not show it.
  • The alcohol is shown taking its proton back from the solvent or on work-up.

Other pathways this class runs by

  • Acid also removes these groups, by protonating the oxygen instead, and the more hindered silyl groups need it.

A class is not one pathway. Which of these runs depends on the substrate, the solvent and what else is in the flask, and the drawing above does not decide that for you.

Run it on your own structures

Enter the reactants and the product you expect. If the transformation is one the engine can perform and this pathway reaches that product from those structures, it is drawn on them — with the arrows on the right atoms and the intermediates you would actually pass through. If it does not reach the product, you are told that instead of being shown a drawing that does not apply.