[MissPhosgene]

Hello,

    I'm not sure if my answer to the attached question is right. Can someone let me know if it is wrong so I can re-think my answer? I don't have access to the journal that the referenced paper is in so I can't verify it myself.

Thanks!

I forgot to add... the question gives a formula for the product: C14H19NOS

[MissPhosgene]

I will give you a molesnack in exchange for an answer....

[orgopete]

That appears to be a rational product. Acetonitrile can open an episulfonium salt to give the anti stereochemistry. The intermediate can react with water to give the suggested amide. I don't know what mercury is doing in this reaction though.

[MissPhosgene]

Thanks Orgopete! I gave you a molesnack . I am not so sure about what mercury does either, which is why I couldn't tell if my answer is correct. It seems like it actually might retard the reaction because it could coordinate with the alkene thus rendering it less electron rich.

Do you have access to the paper? I wonder what they got in terms of yield and side-products.

[AWK]

Give always correct citation - at least one author Zefirov an correct journal Zh. Org. Khim.
Unfortunately I can see in Springer publisher only the last decade of Russian Journal of Organic Chemistry (this is an English equivalent name)

[MissPhosgene]

AWK, I'm sorry. I copied it directly out of my textbook. I will be more careful and I appreciate your suggestion. I will look more carefully into references so I can get authors, etc. when I ask again.

[AWK]

This is direct copy from Carey & Sundberg book

[MissPhosgene]

 My book does not have the names of authors coherently from page 1271 through 1286. A bunch of the pages at the end got damaged because the binding broke, they got ripped, book binder re-bound it, and fixed up the damaged pages so the new spine could get glued properly.

Like I said, I'm sorry. If I can't clearly read author names in the text book, I will search for them before posting. I will post author names next time I need to post a reference. That's the best I can do...

I am also very sorry for making a type-o. Actually, there are two in my post: one in the name of the journal and another in the name of the textbook. I will be sure to be more careful and review what I have written before posting it!

Next post = Improvement!

Best Regards

[MissPhosgene]

I re-posted my question so now all the information it contains is correct and free of type-os.

[AWK]

OK
in Russian version pages 1593-1598

[orgopete]

I wonder if the mercury is present to tie up the chlorides as insoluble HgCl₂. That would allow acetonitrile to open the episulfonium salt which might not be happening otherwise? Just guessing.

[Doc Oc]

Could it also be used to activate the alkene?  LiClO4 has been used for epoxide opening, maybe the mercurium loses an acetate and needs a push to open.  I don't know how nucleophilic MeCN or the PhSCl are in relation to an unactivated alkene though, this is purely hand-waving.

[MissPhosgene]

Cyrillic is pretty looking.

J-bone and Orgopete: I think you both make excellent points. The reaction mixture does not seem as though it will act one way or was very tediously planned out. I searched the reaction in scifinder and almost all of the hits I got went to the above listed journal (a few different issues). I suppose it is not widely used.

I will post a yield if I can find one. AWK, since you have access to the paper, would you mind putting up the yield if I can't find it? Do the authors discuss the mechanism of the reaction or why that choice or reagents was made?

PhSCl is reactive to an unactivated alkene, but acetonitrile wouldn't be. There are many examples of electrophilic sulfur reagents adding to alkenes (same with Selenium). People think that PhSCl adds via a bridged cation in a very similar way to how mercury diacetate would add. I don't know how true that is... it seems to be a good rationalization of the stereochemistry or reactions between alkenes and such reagents, but I haven't found any papers which detail the kinetics/mechanism.

That's what confused me... based on what I know about type of reactivity of electrophilic sulfur and mercury I would assume that they would compete for the alkene. It could be possible that the mercury adds faster than the sulfur reactant and that the bridged mercurium gets opened by LiClO4? Many things sound reasonable for that reaction... Precipitation of HgCl2 would certainly drive the reaction as well...

[MissPhosgene]

Could it be possible for mercury to coordinate with the alkene, rendering it activated to attack by acetonitrile? Upon attack by acetonitrile, mercury can now coordinate with the S in PhSCl activating that for reaction? The thing with that is stereochemistry. It would have to be an insertion of S into the C-Hg bond. That could be partly driven by transfer of Cl- from S to Hg.  - My advisor. He thinks the reaction is somewhat bogus.

I wish I knew as much as him....

[hohoshark]

it is the proposed mechanism, i think