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Acid-Catalyzed Ring-Opening of Epoxides02:24

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Epoxides that are three-membered ring systems are more reactive than other cyclic and acyclic ethers. The high reactivity of epoxides originates from the strain present in the ring. This ring strain acts as a driving force for epoxides to undergo ring-opening reactions either with halogen acids or weak nucleophiles in the presence of mild acid. The acid catalyst converts the epoxide oxygen, a poor leaving group, into an oxonium ion, a better leaving group, making the reaction feasible. The...
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Base-Catalyzed Ring-Opening of Epoxides02:26

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Due to their highly strained structures, epoxides can readily undergo ring-opening reactions through nucleophilic substitution, either in the presence of an acid or a base. The nucleophilic substitution reactions in the presence of acid are called acid-catalyzed ring-opening reactions, and nucleophilic substitution reactions in the presence of a base are called base-catalyzed ring-opening reactions. Epoxides undergo base-catalyzed ring-opening reactions in the presence of a strong nucleophile...
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ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH301:11

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All ortho–para directors, excluding halogens, are activating groups. These groups donate electrons to the ring, making the ring carbons electron-rich. Consequently, the reactivity of the aromatic ring towards electrophilic substitution increases. For instance, the nitration of anisole is about 10,000 times faster than the nitration of benzene. The electron-donating effect of the methoxy group in anisole activates the ortho and para positions on the ring and stabilizes the corresponding...
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meta-Directing Deactivators: –NO2, –CN, –CHO, –⁠CO2R, –COR, –CO2H01:13

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All meta-directing substituents are deactivating groups. These substituents withdraw electrons from the aromatic ring, making the ring less reactive toward electrophilic substitution. For example, the nitration of nitrobenzene is 100,000 times slower than that of benzene because of the deactivating effect of the nitro group. The first step in an electrophilic aromatic substitution is the addition of an electrophile to form a resonance-stabilized carbocation. The energy diagrams for...
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Cycloadditions are one of the most valuable and effective synthesis routes to form cyclic compounds. These are concerted pericyclic reactions between two unsaturated compounds resulting in a cyclic product with two new σ bonds formed at the expense of π bonds. The [4 + 2] cycloaddition, known as the Diels–Alder reaction, is the most common. The other example is a [2 + 2] cycloaddition.
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Redox-Tunable Ring Expansion Enabled By A Single-Component Electrophilic Nitrogen Atom Synthon.

Patrick Q Kelly1, Nikki R Keramati1, Kate R Kaplin1

  • 1Department of Chemistry, University of Chicago, Chicago, IL 60637, United States.

Angewandte Chemie (International Ed. in English)
|November 11, 2024
PubMed
Summary

A novel reagent, DNIBX, enables controlled nitrogen atom installation in organic synthesis. This method allows for divergent ring expansions of indanone β-ketoesters, yielding diverse heterocycles under thermal or photochemical conditions.

Keywords:
heterocycleshypervalent iodinereaction mechanismsring expansionssynthetic methods

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Area of Science:

  • Organic Chemistry
  • Synthetic Methodology
  • Heterocyclic Chemistry

Background:

  • Controlled nitrogen atom installation is crucial for skeletal editing.
  • Existing nitrogen atom sources limit progress in synthetic transformations.
  • Novel reagents are needed to advance nitrogen incorporation strategies.

Purpose of the Study:

  • To introduce a new reagent, DNIBX, for electrophilic nitrogen atom installation.
  • To explore the divergent reactivity of DNIBX-derived adducts in organic substrates.
  • To investigate the synthesis of diverse heterocycles via ring expansion reactions.

Main Methods:

  • Development of DNIBX (dibenzoazabicycloheptadiene) as a novel nitrogen atom source.
  • Electrophilic amination of indanone β-ketoesters using DNIBX.
  • Thermal and photochemical activation of resulting adducts to induce ring expansion.

Main Results:

  • DNIBX successfully installed the dibenzoazabicycloheptadiene moiety onto organic substrates.
  • Aminated indanone β-ketoesters underwent divergent ring expansions.
  • Different oxidation states of heterocycles were produced under thermal versus photochemical activation.
  • Mechanistic pathways for both transformations were elucidated.

Conclusions:

  • DNIBX provides a versatile platform for controlled nitrogen incorporation.
  • The study demonstrates a novel route to diverse heterocycles with tunable oxidation states.
  • Comparison with other nitrogenous precursors highlights the unique reactivity of DNIBX adducts.