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DOS fragments grow hits in several directions at once

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A modular diversity-oriented fragment library gave crystallographic hits on several proteins and then short, cheap sequences to many analogues, including a first covalent PBP3 fragment.

Source

Demonstration of the utility of DOS-derived fragment libraries for rapid hit derivatisation in a multidirectional fashion

Kidd SL, Fowler E, Reinhardt T, et al. · Chemical science · 2020

doi.org/10.1039/d0sc01232gRead the full paper ↗18 citationscc by

What they did

Authors screened a racemic DOS fragment set (500 mM in d6-DMSO) by X-ray crystallography, then used designed exit vectors—amide couplings, click chemistry, Cu(I) lactonizations—to elaborate hits such as the PBP3 covalent binder 1.

What they found

Compound 1 was the first binder after ~1300 prior fragment soaks on PBP3, covalently linking Ser294. Up to 14 analogues per hit were accessible; only p-fluoro analogue 28 of nine aromatics soaked into CFI crystals; 1,4-isoxazole 29 bound but 1,5-isomer 30 did not.

The limits

What it doesn't show

The paper does not report optimized cellular potency or a clinical candidate—only early crystallographic hits and synthetic tractability.

Key terms

DOS
Diversity-oriented synthesis aimed at skeletally diverse, 3-D small molecules.
Fragment-based drug discovery
Screening small, weak binders then growing/linking them into potent ligands.
PBP3
Penicillin-binding protein 3, a bacterial cell-wall transpeptidase.
Exit vector
A designed site on a fragment where chemistry can grow the molecule.
Covalent binder
A fragment that forms a bond to an active-site residue (here Ser294).

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PBP3 hit 1 is notable because it was:

Common questions

What protein gave the first covalent DOS hit?

PBP3, compound 1 (PDB 6Y6Z).

How was the library screened?

Racemic, 500 mM in d6-DMSO, by X-ray (XChem).

How many analogues per hit were typically made?

Up to 14 in short sequences.

Which aromatic substitution soaked for CFI?

Only the p-fluoro analogue 28 of nine.

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