My question is regarding Swern oxidation. Why is the methyl group of the DMSO deprotonated and not directly the red hydrogen atom of the R2-CH-O bond deprotonated? Shouldn't it be that oxygen more electronegative (stronger -I effect) than sulfur and shouldn't that make that corresponding hydrogen atom more acidic? Or is it perhaps that sulfur has a positive charge and therefore acts as a stronger electrophile that attracts the electrons from carbon and therefore its hydrogen groups are more acidic?

Mechanism in Question

  • $\begingroup$ Related: ylide stability. Also, mechanisms usually show the shortest path. Try going your way and see what ends up happening. $\endgroup$ – Eashaan Godbole Jul 17 '19 at 14:06
  • $\begingroup$ If I go my way... I guess a carboanion is built, which is very unstable? But then the electronegative oxygen will take the electrons anyway right? Wouldnt the net effect be the same? Just that there doesnt have to be a second attack? $\endgroup$ – justastudent Jul 17 '19 at 14:11
  • $\begingroup$ The oxygen is electronegative, but is it electron-deficient? $\endgroup$ – Eashaan Godbole Jul 17 '19 at 14:16
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    $\begingroup$ The hydrogen alpha to an oxygen is not generally very acidic at all - consider diethyl ether. The +ve charge on the sulfur makes the proton on the neighbouring carbon pretty acidic $\endgroup$ – Waylander Jul 17 '19 at 14:17
  • $\begingroup$ S increases acidity more than O to begin with, compare sulfides and ethers; and the positive charge makes the proton next to S even more acidic. $\endgroup$ – orthocresol Jul 17 '19 at 16:49

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