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Use of sulfonyl fluorides to produce sulfonyl Phosphonates

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Babcock_Hall:
Won Bum Jang , Hyoung Joon Jeon & Dong Young Oh∗ (1998) Direct Sulfonylation of Lithiated Alkyl Phosphonates with Benzenesulfonyl Fluoride; Facile Method for Preparation of α-Sulfonyl Alkyl Phosphonates and Vinyl Sulfones, Synthetic Communications, 28:7,
1253-1256, DOI: 10.1080/00397919808005967

This paper uses lithium bis(trimethylsilyl)amide (lithium hexamethyldisilazane) to remove a proton from diethyl methylphosphonate (they are not far apart in pKa values).  The use of a sulfonyl fluoride, not chloride is critical.  This paper has not been followed up, except in two patents (at least based upon my searching).  How general is this method regarding the group bound to sulfur?  One potential problem I can see is that if there is an acidic proton on the sulfonyl fluoride, there could be a problem, and α-hydrogens relative to a sulfonyl have a broad range of pKa values, with the highest being about 31.  Cyclopropanesulfonyl fluoride is available, and cyclopropanyl would be one of the R groups of interest.  Biphenyl is another R group of interest.

rolnor:
I have done a lot of chemistry on cyclopropanes. The method you have can be really good, it can be a problem with the acidic  proton on the sulphonylfluoride but you have to try, the reaction with the sulphonylfluoride can be very fast so maybe no problem. The product will have even more acidic protons with two activating groups.
If you can buy cyclopropane disulfide you can react this in a similar fascion to get the sulfide  and then you can oxidize this to the sulphone as you have shown. Thats a very generall method probably, also for the biphenyl I think. Disulfides are soft nice electrophiles with no acidic protons. I think you can buy a lot of them. They are also easy to make by alkaline iodine oxidation of sulfides. (Stench-warning, I used thiophenol…)
Here are some vendors: https://pubchem.ncbi.nlm.nih.gov/compound/Dicyclopropyldisulfide

wildfyr:
Sulfonyl fluorides are very strong EWG, I think you want to try to go for a kinetically controlled reaction if possible, because that proton is quite acidic. But yeah the chances of making a mess are probably not small.

You very seldom see alkyl sulfonyl fluorides, much more common is aryl sulfonyl fluorides followed by unsaturated ones (like ethene sulfonyl fluoride), probably for this precise reason. If you look at SuFEx chemistry you can see a ton of example of the unsaturated ones.

Source: I made alkyl sulfonyl fluorides during my PhD.

Babcock_Hall:
Thank you both very much.  Although S-cyclopropyl* is the first target that I have in mind, I would obviously like to be able to create as much structural diversity as possible. I don't see a problem with the S-biphenyl group.**  Two of the other sulfonyl fluorides that are commercially available are 2-pyramidinyl and 2-thiophenyl.  Do either of these look problematic for conversion into a sulfonyl phosphonate?

Regarding the S-CH2-P group in the product, its acidity is higher than the acidity of diethyl methylphosphonate, yet the method worked for phenylsulfonyl fluoride.  I take this as an encouraging sign.

*In another thread we discussed using S-cyclopropylsulfinate as the starting material for a sulfonyl phosphonate.  I still think that this idea has merit.
**EDT (added much later) I suspect that phenoxyphenyl would be OK, also.

rolnor:
It can be straightforward. If not the disulfide approach can be useful. You wright 2-thiophenyl, is that the free mercaptane? The 2-pyrimidanyl seems OK. Yes, I commented on the acidic protons in the product, the method does not seem to be so sensitive to this.

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