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In another question, I mentioned that O-protonation of an enolate followed by tautomerization may lead to increased amounts of the thermodynamic product over the kinetic product (when those are different species).

The idea that the oxygen is likely protonated first has been discussed previously.

The way, I think, to get the most kinetic product is to use a bulky acid that would do C-protonation rather than O-protonation (assuming sterics explain the difference in kinetic/thermo product). The proton would have to be a softer electrophile, i.e. less positively charged than a proton from a stronger acid.

To continue with the example I gave in the previous question, I think it's likely that C-protonation would look like this, where the major product would be the kinetic product:

enter image description here

So my question is: are there acids that are known to specifically protonate the carbon of an enolate rather than the oxygen? I was thinking maybe BHT would work. Or maybe the thiol analogue of BHT - yes, it would be more acidic than BHT, but it would also be a softer nucleofuge than the BHT anion. This reasoning works with alkyl halides, i.e. softer leaving group = more C-attack, but I'm not sure if the same goes here.

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  • $\begingroup$ I guess $\sigma ^{*} _{\ce{S-H}}$ would be lower in energy than $\sigma ^{*} _{\ce{O-H}}$, so even though BHT would a weaker acid than the equivalent thiol, the thiol would still have better HOMO-LUMO overlap with carbon and lower $\delta +$ on the hydrogen. $\endgroup$
    – SendersReagent
    Mar 24, 2016 at 16:13
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    $\begingroup$ I think it's reasonable to extend the logic of O- vs. C-alkylation to protonation. I don't see any good way of proving the results of the experiment though. $\endgroup$
    – jerepierre
    Mar 24, 2016 at 18:15
  • $\begingroup$ @jerepierre What do you mean you don't see any good way of proving the results? You mean that even if the results came out as I expected, it wouldn't be definitive that it happened the way I described it? $\endgroup$
    – SendersReagent
    Mar 24, 2016 at 19:44
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    $\begingroup$ Trap it as the silyl ketene acetal and then protonate that, eg. doi.org/10.1016/S0040-4039(00)84541-4 $\endgroup$
    – Organic Chemistry Explained
    Nov 25, 2018 at 3:22
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    $\begingroup$ You might use tert-butyl bromide as your "acid" source via an E2 elimination. $\endgroup$
    – user55119
    Apr 22, 2020 at 23:02

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