What is the reaction mechanism here?

I guess the $\ce{SnCl2}$ reduces $\ce{NO2}$ to $\ce{NH2}$ but then what happens?

enter image description here

  • 2
    $\begingroup$ I'm thinking there is a retro-Diels-Alder in there somewhere $\endgroup$
    – Waylander
    Aug 4 '20 at 11:05
  • $\begingroup$ Can you please show me how exactly, I tried didn’t work $\endgroup$
    – lidya
    Aug 4 '20 at 15:36
  • $\begingroup$ If I knew exactly I would post an answer. I do not have database access to find the paper where this is reported. $\endgroup$
    – Waylander
    Aug 4 '20 at 15:39
  • $\begingroup$ @Waylander A side-note about the speculated occurrence of a retro-DA, I'm sceptical; because in the starting material, I count 12, but in the product only 11 carbon atoms. $\endgroup$
    – Buttonwood
    Aug 4 '20 at 21:11
  • $\begingroup$ @Buttonwood Count again! There are 13 in the SM $\endgroup$
    – Waylander
    Aug 4 '20 at 22:15

This reaction was conducted by Ho and Liao1. Nitro compound 1 is reduced to the nitroso compound 2 which undergoes a [3+3] electrocyclization to form 3 (4). Tautomerization of 4 to 5 is followed by a retro-"Diels-Alder" reaction to open to 6. Conjugate addition of the nitrogen to the unsaturated aldehyde moiety of 6 to afford dihydro pyridine 7. Tautomerization of 7 to 8 is followed by the loss of acetaldehyde. [Structures are from the paper; my numbering.] enter image description here

ADDENDUM: The mechanism provided in the paper does not address a number of stereochemical issues. Nitro compound 1 is obviously formed as an endo-Diels-Alder product between (E)-(2-nitrovinyl)benzene and 1,3-cyclopentadiene. The bicyclic compound 3 (4) must have a cis-fusion given the mechanism of the [3+3]-electrocyclization (23) (vide infra). However, the stereochemistry arising from the retro-Diels-Alder reaction would not be expected to kinetically form the (Z,Z)-diene 6 but rather the (E,Z)-isomer 6a. Clearly, 6a is incapable of cyclization as prescribed. But 6a is a masked, vinylogous malonaldehyde that is susceptible to enolization and isomerization to 6b or 6c. While 6c can cyclize by the reported procedure of conjugate addition, there is also the probability that ring closure occurs by electrocyclization of 6b.

  1. Tse-Lok Ho and Po-Yau Liao, Tetrahedron Lett., 1994, 35, 2211. DOI:10.1016/S0040-4039(00)76799-2
  • $\begingroup$ I already upvoted your answer. But I'm curious about the elimination of acetaldehyde. What is the driving force? Is that mean $\beta$-amino acids are prone to leave $\ce{CO2}$? $\endgroup$ Aug 9 '20 at 17:00
  • 1
    $\begingroup$ @Mathew: Wouldn't be surprised if the zwitterion of beta-aminopropionic acid gives ethylene under some set of conditions. In the present case, becoming aromatic is certainly worth something. If you mix 9 and 10 under some set of conditions, I'd be surprised to see any 8. $\endgroup$
    – user55119
    Aug 9 '20 at 17:25
  • $\begingroup$ @Mathew: I've thinking about your question again. There are stannic salts generated in the reduction. Perhaps they facilitate loss of acetaldehyde. So the question is, will Sn(IV) catalyze the addition of acetaldehyde to 3-phenylpyridine (9) to form 8? $\endgroup$
    – user55119
    Aug 9 '20 at 20:29
  • $\begingroup$ Might not. Otherwise, the last elimination step would have been reversible. I think gaining aromatically is a very good point for the elimination. In my experience, I didn't find any decomposition of $\beta$-amino acids during their synthesis. $\endgroup$ Aug 9 '20 at 21:33
  • 1
    $\begingroup$ Mostly a quibble, but I was wondering if the last step could be conveniently drawn as such. A bit reminiscent of beta-ketoacid decarboxylation. i.stack.imgur.com/Byn29.jpg (cc @MathewMahindaratne) $\endgroup$
    – orthocresol
    Aug 12 '20 at 7:01

Your Answer

By clicking “Post Your Answer”, you agree to our terms of service, privacy policy and cookie policy

Not the answer you're looking for? Browse other questions tagged or ask your own question.