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Radical Reactivity: Steric Effects01:10

Radical Reactivity: Steric Effects

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The presence of electron-donating, electron-withdrawing, or conjugating groups adjacent to a radical center, imparts electronic stabilization to the radicals. Examples of such electronically-stabilized radicals are triphenylmethyl, tetramethylpiperidine‐N‐oxide, and 2,2‐diphenyl‐1‐picrylhydrazyl. These radicals are remarkably stable and are known as persistent radicals. Some of the persistent radicals can even be isolated and purified.
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Radical Substitution: Allylic Bromination01:27

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In organic synthesis, the formation of products can be altered by changing the reaction conditions. For example, a dibromo addition product is formed when propene is treated with bromine at room temperature. In contrast, propene undergoes allylic substitution in non-polar solvents at high temperatures to give 3-bromopropene. In order to avoid the addition reaction, the bromine concentration must be kept as low as possible throughout the reaction. This can be achieved using N-bromosuccinimide...
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Benzene to 1,4-Cyclohexadiene: Birch Reduction Mechanism01:18

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Birch reduction uses solvated electrons as reducing agents. The reaction converts benzene to 1,4-cyclohexadiene. The reaction proceeds by the transfer of a single electron to the ring to form a benzene radical anion. This anion is highly basic—it abstracts a proton from the alcohol to form a cyclohexadienyl radical. Another single electron transfer gives the cyclohexadienyl anion. A proton transfer from the alcohol forms 1,4-cyclohexadiene. Since this reduction occurs via radical anion...
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Radical Formation: Elimination00:51

Radical Formation: Elimination

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Another method of radical formation is the elimination process. It is the opposite of the addition route and is driven by the instability of the radical. For example, as depicted in Figure 1, dibenzoyl peroxide yields a pair of unstable radicals upon homolysis. Given its instability, this radical spontaneously undergoes elimination via a C–C bond cleavage to form a relatively more stable phenyl radical. The mechanism involves cleavage of the bond between the α and β positions...
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E1 Reaction: Stereochemistry and Regiochemistry02:43

E1 Reaction: Stereochemistry and Regiochemistry

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One of the critical aspects of the E1 reaction mechanism, as also observed in E2, is the regiochemistry, with multiple regioisomers obtained as products. In the example discussed, the presence of water as a weak base favors elimination over substitution to generate two alkenes. Given that alkenes’ stability increases with the number of alkyl groups across the double bond, typically, E1 reactions lead to the Zaitsev product, for this is more substituted and stable than the Hofmann product.
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Alkylation of β-Diester Enolates: Malonic Ester Synthesis01:14

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Malonic ester synthesis is a method to obtain α substituted carboxylic acids from ꞵ-diesters such as diethyl malonate and alkyl halides.
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Related Experiment Video

Updated: Jul 8, 2025

Preparation of Enantiopure Non-Activated Aziridines and Synthesis of Biemamide B, D, and epiallo-Isomuscarine
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Benzylic Radical Stabilization Permits Ether Formation During Darobactin Biosynthesis.

Austin M Woodard1,2, Francesca Peccati3, Claudio D Navo3

  • 1Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA.

Biorxiv : the Preprint Server for Biology
|December 11, 2023
PubMed
Summary

Researchers explored the enzymatic modification of the antibiotic darobactin A, creating new variants by altering its precursor peptide. This study reveals insights into radical S-adenosyl methionine enzyme catalysis and informs future scaffold engineering.

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Area of Science:

  • Biochemistry
  • Synthetic Biology
  • Medicinal Chemistry

Background:

  • Darobactin A is a Gram-negative selective antibiotic with a unique fused bicyclic structure and mechanism of action.
  • Darobactin is a ribosomally synthesized and post-translationally modified peptide (RiPP) requiring enzymatic maturation.
  • The maturation process involves a radical S-adenosyl methionine (rSAM)-dependent enzyme (DarE) that installs ether and C-C crosslinks.

Conclusions:

  • DarE exhibits significant flexibility in installing ether and C-C crosslinks, enabling the generation of diverse darobactin scaffolds.
  • The study provides mechanistic insights into rSAM-dependent crosslinking, linking radical stability to ether formation.
  • Understanding DarE's substrate engagement and catalytic principles facilitates rational engineering of the darobactin scaffold for potential therapeutic applications.