October 19, 2021, 04:51:50 AM
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Topic: Contemporary O-Chem  (Read 222 times)

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Offline phth

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Contemporary O-Chem
« on: October 13, 2021, 07:06:19 PM »
Hello,
I'm trying to think about recent developments in synthesis that are novel and useful to know. Was wondering if you have come across such a reaction and wouldn't mind sharing a link.

1) nitrogen deletion reagent:
https://www.chemistryworld.com/news/nitrogen-deletion-reaction-offers-new-way-to-think-about-molecular-editing/4013684.article

Offline rolnor

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Re: Contemporary O-Chem
« Reply #1 on: October 14, 2021, 02:31:07 AM »
I think maybe the organocatalysis that gave the Nobel prize this year can be one such reaction-typ.

The nitrogen-deletion is interesting, it seems limiting that one of the groups need to be radical-stabilizing, and it would be nice to see how selective the reagent is. It could be a really nice way to make carbon-carbon bonds.

Offline Babcock_Hall

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Re: Contemporary O-Chem
« Reply #2 on: October 14, 2021, 09:29:21 AM »
https://pubs.acs.org/doi/10.1021/acs.orglett.0c01549
The only thing I can think of at the moment might be a bit parochial (meaning that it might be a little too specialized), but I was just reading a paper on making glycosides with unprotected α-D-Glucose using Mitsunobu chemistry.
« Last Edit: October 14, 2021, 09:49:28 AM by Babcock_Hall »

Offline rolnor

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Re: Contemporary O-Chem
« Reply #3 on: October 14, 2021, 09:38:01 AM »
Very interesting Babcock, nice paper! The choice of solvent can be so critical, it shows that we know very little about whats going on really.

Offline Babcock_Hall

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Re: Contemporary O-Chem
« Reply #4 on: October 14, 2021, 09:40:48 AM »
Thank you; I was thinking about starting a thread on it, anyway.  There are a number of functional groups that are tolerated.  How student-friendly do you think that the procedure is?  I can easily envision a reaction I would like to do.

Offline wildfyr

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Re: Contemporary O-Chem
« Reply #5 on: October 17, 2021, 11:56:13 AM »
I think copper click of azide/alkyne (CuAAC) has become incredibly important. You see triazoles everywhere. Its in both medicinal chemistry, and used in materials science.

Its very easy to do as well, you can buy a relatively easy to handle azide like benzyl azide, and various propargyl alcohol/esters and the do the classic CuSO4, ascorbic acid, water and tert butanol and get a true click reaction. Works in a scint vial. Purification is just LL separation and evaporation. You can look for the loss of azide and alkyne by FTIR, very distinctive peaks.

Its 20 years old but "recent" is relative in chemistry :-P.

You could also make thiol-ene gels as a bit of materials science. Run it as a photochemistry experiment, you can use sunlight!

In terms of some really novel reactions at a higher level, I think the usage of aryl fluorosulfates for carbon-carbon bond formation is pretty unique and new. Fluorosulfates and related compounds also undergo a fascinating reactivity blend with various nucleophiles depending on conditions.

https://pubs.acs.org/doi/10.1021/acs.orglett.5b00654 (just one small example, google fluorosulfates and youll see plenty more)

https://onlinelibrary.wiley.com/doi/abs/10.1002/ange.201611048 reactivity of SOF4 type materials. The reactivity of nucleophiles with plain fluorosulfates is interesting too.
« Last Edit: October 17, 2021, 12:16:47 PM by wildfyr »

Offline rolnor

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Re: Contemporary O-Chem
« Reply #6 on: October 17, 2021, 02:18:12 PM »
Very nice with the fluorosulphates, maybe they are more reactive because the fluoro is so much less bulky than trifluoromethyl? Must be great in industrial scale when you dont need ligands and can run in normal atm. plus water as solvent, really impressive.

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