Comments on: Alkene Reactions: Ozonolysis https://www.masterorganicchemistry.com/2013/04/23/alkene-reactions-ozonolysis/ Thu, 01 Aug 2024 12:50:51 +0000 hourly 1 https://wordpress.org/?v=6.6.2 By: Mu Hsuan-Jung https://www.masterorganicchemistry.com/2013/04/23/alkene-reactions-ozonolysis/#comment-701834 Thu, 01 Aug 2024 12:50:51 +0000 https://www.masterorganicchemistry.com/?p=7238#comment-701834 Thank you for your reply! I tried to draw the mechanism for the oxidative work up of ozonolysis of tetrasubstituted alkene with H2O2. After the ozonide being cleaved into a ketone and a Criegee intermediate, I couldn’t use water to do proton transfer since there’s no H on the carbon, so I tried H2O2 and it seemed like there would be an equivalent of O2 released, but I’m not sure if I’m right. (I saw an article on Chemistry LibreTexts and it says the product would be 2 ketones.)

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By: James Ashenhurst https://www.masterorganicchemistry.com/2013/04/23/alkene-reactions-ozonolysis/#comment-701629 Tue, 30 Jul 2024 15:25:19 +0000 https://www.masterorganicchemistry.com/?p=7238#comment-701629 In reply to Mu Hsuan-Jung.

You could perform the workup using either using reductive conditions (best) or oxidative. Usual procedure is just to add dimethylsulfide at low temperature to destroy excess ozonide and then let it warm to room temperature.

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By: Mu Hsuan-Jung https://www.masterorganicchemistry.com/2013/04/23/alkene-reactions-ozonolysis/#comment-701224 Fri, 26 Jul 2024 14:58:58 +0000 https://www.masterorganicchemistry.com/?p=7238#comment-701224 I have a question about the oxidative workup. What if I use tetrasubstituted alkene in the reaction?

I’ve seen the mechanism of both reductive and oxidative workup in the article but it seems like only the reductive one is possible because the extra oxygen in ozonide can leave with DMS, while in the oxidative one there’s one more oxygen needed to form the OH in the carboxylic acids. Now in the case of tetrasubstituted alkene, there’re no hydrogen to leave for the carbon to allow one more OH group on it. Is it right that I can’t use oxidant to workup the ozonide of tetrasubstituted alkene?

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By: James Ashenhurst https://www.masterorganicchemistry.com/2013/04/23/alkene-reactions-ozonolysis/#comment-634460 Mon, 01 Aug 2022 23:28:22 +0000 https://www.masterorganicchemistry.com/?p=7238#comment-634460 In reply to will k.

Yes, I would give it a shot. If you have access to the Sharpless AD-Mix that would be a good thing to try since the bulky ligands should keep your osmium away from the bulkier alkene.
See here:
https://hwpi.harvard.edu/files/myers/files/23-sharpless_asymmetric_dihydroxylation_reaction.pdf

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By: will k https://www.masterorganicchemistry.com/2013/04/23/alkene-reactions-ozonolysis/#comment-634459 Mon, 01 Aug 2022 23:06:55 +0000 https://www.masterorganicchemistry.com/?p=7238#comment-634459 Thank you for your suggestion, that is certainly something that might work. I should have clarified that my problem involved a cyclic tetrasubstituted alkene and an internal disubstituted alkene. I want the less substituted alkene to be cleaved and the tetrasubstituted one to be left alone. Will my aforementioned dihydroxylation followed by cleavage of the vicinal diol work?

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By: James Ashenhurst https://www.masterorganicchemistry.com/2013/04/23/alkene-reactions-ozonolysis/#comment-634444 Mon, 01 Aug 2022 20:25:58 +0000 https://www.masterorganicchemistry.com/?p=7238#comment-634444 In reply to will k.

Good question. You are indeed correct that greater alkene substitution favors a higher rate of ozonolysis,

Is your problem concerning selectivity on a molecule with multiple alkenes? Is this something that could be avoided through, say, a later-stage reduction of an alkyne to a cis or trans alkene (alkynes are generally slow to cleave with ozonolysis).

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By: will k https://www.masterorganicchemistry.com/2013/04/23/alkene-reactions-ozonolysis/#comment-634428 Mon, 01 Aug 2022 13:49:57 +0000 https://www.masterorganicchemistry.com/?p=7238#comment-634428 It is my understanding that ozonolysis favours more substituted alkenes. Are there any reactions that favours the cleavage of less substituted alkenes? I think dihydroxylation favours less substituted alkenes, the resulting vicinal diols can then be cleaves with sodium periodate. However, I am not certain if my thinking is correct, if I’m wrong are there any other
methods?

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By: Aerosols: Mechanisms of Mischief – Berkeley Scientific https://www.masterorganicchemistry.com/2013/04/23/alkene-reactions-ozonolysis/#comment-609959 Tue, 02 Nov 2021 02:56:03 +0000 https://www.masterorganicchemistry.com/?p=7238#comment-609959 […] Ashenhurst, J. (2013, April 23). Alkene reactions: ozonolysis. Master Organic Chemistry. https://www.masterorganicchemistry.com/2013/04/23/alkene-reactions-ozonolysis/ […]

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By: James Ashenhurst https://www.masterorganicchemistry.com/2013/04/23/alkene-reactions-ozonolysis/#comment-605303 Thu, 09 Sep 2021 18:01:20 +0000 https://www.masterorganicchemistry.com/?p=7238#comment-605303 In reply to Dolapo.

Methanal (formaldehyde) is quickly oxidized by H2O2 to give carbonic acid which itself loses water to give CO2 (carbon dioxide)

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By: Dolapo https://www.masterorganicchemistry.com/2013/04/23/alkene-reactions-ozonolysis/#comment-605013 Wed, 01 Sep 2021 05:28:27 +0000 https://www.masterorganicchemistry.com/?p=7238#comment-605013 Ozonolysis of 3 methylbut-1-ene in the presence of H202

One of the products is methanal my note here in textbook concert it into CO2
Pls why

And not methanoic acid

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