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Gabriele Laudadio @glaudadio.bsky.social · 1d

I totally agree... MOF has been in the shortlist for a while...

Gabriele Laudadio @glaudadio.bsky.social · 19d

Since the review is about the modular nature of these platforms and how they were exploited in the literature, puzzle pieces came up pretty naturally. My biggest problem was filling the lab bench in back 😬

2

Gabriele Laudadio @glaudadio.bsky.social · 19d

Thanks for the kind words! The idea of the e-chem robot dreaming about automating itself was something that was bugging my head for a while! That was where the whole concept started :)

1

Gabriele Laudadio @glaudadio.bsky.social · 23d

I had a lot of fun designing the cover. It started from a simple concept: I wanted to revisit a classic in sci-fi literature. My wife sketched the idea for me, the rest is history :) #chemsky

1 3

Gabriele Laudadio @glaudadio.bsky.social · 23d

Interested in automating your electrochemical reaction? Check our tutorial review on automation in synthetic organic electrochemistry, online open access on Chemistry Methods

Modules description and relevant examples, all in one document!

chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/...

Automating Synthetic Organic Electrochemistry: Concepts and Advancements

A tutorial review on how to build an automated electrochemical flow platform, including the most relevant progresses and the future directions of the field, is studied.

chemistry-europe.onlinelibrary.wiley.com

1 1 10

Gabriele Laudadio @glaudadio.bsky.social · 28d

And this is the story of how we turned something theoretically really cool into something synthetically useful. An elusive intermediate chased for 60 years :)

(12/12)

1

Gabriele Laudadio @glaudadio.bsky.social · 28d

It seems that without the electrochemical polishing of the magnesium electrode, the reaction cannot take place. Weird enough, a reduction at the anode.

(11/n)

1 1

Gabriele Laudadio @glaudadio.bsky.social · 28d

Turned out that it's the Mg of the sacrificial anode that does the job (as Perichon hypothesized)! It has sufficient redox potential to do it, but the constant refresh of the Mg surface is crucial to the success of the reaction. (10/n)

1

Gabriele Laudadio @glaudadio.bsky.social · 28d

And finally, we landed on the mechanistic investigation. We proved the radical formation and the radical attack (see the key experiment with beta-caryophyllene).

But if the potential required is so low, how can this work?? (9/n)

1

Gabriele Laudadio @glaudadio.bsky.social · 28d

During the scope we identified some key requirements for successful substrates... (8/n)

1 2

Gabriele Laudadio @glaudadio.bsky.social · 28d

Then we went for the scope, Yifan and Sulekha (the real stars of this project) unleashed their creativity and they worked with some wild monsters... Along with a two-step-one-pot system to reduce the enamine to perform hydroaminomethylation and consecutive homologation (7/n)

1

Gabriele Laudadio @glaudadio.bsky.social · 28d

So we spent some time on it, and after a while, we achieved our desired hydroformylated product. Interestingly, all the thermal controls did not work. (6/n)

1

Gabriele Laudadio @glaudadio.bsky.social · 28d

... Why is this radical so elusive? While HAT intermediates are relatively easy to obtain, direct SET reduction is a completely different deal, just look at the CV. This is the reason why it is one of the solvents of choice for cathodic reactions. (5/n)

1

Gabriele Laudadio @glaudadio.bsky.social · 28d

But there was somebody else who obtained some dimers from DMF... One of the giants of electrochemistry, Dr. Jacques Perichon.
He observed something weird. His Mg sacrificial electrodes were consumed much more than they should have been... (4/n)

1

Gabriele Laudadio @glaudadio.bsky.social · 28d

In 2012, Shkrob and Marin explored the radiolysis of formamides via EPR, obtaining spectroscopic evidence of a new radical species (Radical X)... They hypothesized that the existence of a reduced species of DMF, which could exist only in its solvated form... (3/n)

1

Gabriele Laudadio @glaudadio.bsky.social · 28d

In 1965, Prof. Bredereck found out that boiling formamides with Li, Na, or K (fun, isn't it?) you may get some weird dimers... (2/n)

1

Gabriele Laudadio @glaudadio.bsky.social · 28d

We are proud to present our work on something really special, appeared in
@ChemRxiv
today. We unlocked the synthetic application of DMF distonic radical anion with electrochemistry!

Interested in the full story? See below! (1/n)

chemrxiv.org/engage/chemr...

1 2 11

Gabriele Laudadio @glaudadio.bsky.social · 28d

And this is the story of how we turned something theoretically really cool into something synthetically useful. An elusive intermediate chased for 60 years :)

(12/12)

Gabriele Laudadio @glaudadio.bsky.social · 28d

It seems that without the electrochemical polishing of the magnesium electrode, the reaction cannot take place. Weird enough, a reduction at the anode.

(11/n)

1

Gabriele Laudadio @glaudadio.bsky.social · 28d

Turned out that it's the Mg of the sacrificial anode that does the job (as Perichon hypothesized)! It has sufficient redox potential to do it, but the constant refresh of the Mg surface is crucial to the success of the reaction. (10/n)

1

Gabriele Laudadio @glaudadio.bsky.social · 28d

And finally, we landed on the mechanistic investigation. We proved the radical formation and the radical attack (see the key experiment with beta-caryophyllene).

But if the potential required is so low, how can this work?? (9/n)

1

Gabriele Laudadio @glaudadio.bsky.social · 28d

During the scope we identified some key requirements for successful substrates... (8/n)

1 1

Gabriele Laudadio @glaudadio.bsky.social · 28d

Then we went for the scope, Yifan and Sulekha (the real stars of this project) unleashed their creativity and they worked with some wild monsters... Along with a two-step-one-pot system to reduce the enamine to perform hydroaminomethylation and consecutive homologation (7/n)

1

Gabriele Laudadio @glaudadio.bsky.social · 28d

So we spent some time on it, and after a while, we achieved our desired hydroformylated product. Interestingly, all the thermal controls did not work. (6/n)

1

Gabriele Laudadio @glaudadio.bsky.social · 28d

... But why is this radical so elusive? While HAT intermediates are relatively easy to obtain, direct SET reduction is a completely different deal, just look at the CV. This is the reason why it is one of the solvents of choice for cathodic reactions. (5/n)

1