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Uphill

A concept cover I have made that could illustrate Pr. David Leigh research on Endergonic synthesis driven by chemical fuelling (see 10.26434/chemrxiv-2023-6nqn3)

Chemical reactions happen naturally, either going smoothly or needing a push. Some reactions release energy easily (exergonic), while others need energy to happen (endergonic). Scientists have used light to drive certain reactions, but it only works for materials that can absorb the light's energy.
Now, there's a new discovery. Researchers found a way to use a special chemical fuel to make a tricky reaction happen. They used a substance called diisopropylcarbodiimide (DIC) to help it along. This made a reaction, called Diels–Alder, occur when it normally wouldn't easily.
They used a "ratchet" mechanism, similar to how tools work, to keep the reaction going in a particular direction, which is opposed to the direction that the reaction woud normally follow. This could be a game-changer in chemistry, offering new ways to create molecules with more control.

Original Scheme

Original Scheme

The substrates of the reactions at the lowest point of the potential energy diagram

The substrates of the reactions at the lowest point of the potential energy diagram

If the reaction can proceed uphill, it is because it is fuelled by diisopropylcarbodiimide (DIC)!

If the reaction can proceed uphill, it is because it is fuelled by diisopropylcarbodiimide (DIC)!

After reacting with DIC, a first intermediate is formed...

After reacting with DIC, a first intermediate is formed...

As the reaction proceeds, it is converted to another intermediate, presumably from the intramolecular cycloaddition of the mixed anhydride

As the reaction proceeds, it is converted to another intermediate, presumably from the intramolecular cycloaddition of the mixed anhydride

Which then reacts one last time to form the final Diels Alder product, higher in energy than the substrates!

Which then reacts one last time to form the final Diels Alder product, higher in energy than the substrates!