Saturday, September 21, 2019

organic chemistry - Mechanism of the oxidation of alcohols with KMnO4


Many oxidising agents, like chromate, dichromate, iodine in NaOH etc. seem to work via ester formation and elimination. For example, chromic acid will react with the OH of alcohol to form a chromate ester, and then this will undergo an E2-like elimination, with a proton abstracted from carbon and loss of leaving group from oxygen.


However it seems that manganate works via a different mechanism. I think this because here: http://www.masterorganicchemistry.com/2015/05/21/demystifying-alcohol-oxidations/


It says in a footnote at the bottom:



"..main exception you’ll encounter is KMnOX4, which likely proceeds through a C-H abstraction/internal return type mechanism followed by collapse of the hydrate to give the new carbonyl."




I don't quite understand this brief summary of the mechanism, could someone expand on it? I don't quite understand what "internal return type mechanism" is refering to - I kind of understand it refers to something a little like the "intimate ion pair" in the SNi mechanism, but haven't been able to find online a more expanded mechanism - many places seem to show it like the case of chromic acid above, and so I am slightly confused as to what mechanism it really follows.



Answer



KMnOX4/OHX Oxidation


KMnO4 Oxidation


HX2CrOX4 Oxidation Jones Oxidation


The two main differences are



  1. HX2CrOX4 Oxidation occurs in acid, KMnOX4 oxidation occurs in base

  2. The source of the nucleophile in the removal of the metal ester. In KMnOX4 oxidation, the Mn ester itself extracts the HX+ from the alcohol carbon, while in HX2CrOX4 oxidation the nucleophile is the solvent.



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