Jove
Visualize
Contact Us
JoVE
x logofacebook logolinkedin logoyoutube logo
ABOUT JoVE
OverviewLeadershipBlogJoVE Help Center
AUTHORS
Publishing ProcessEditorial BoardScope & PoliciesPeer ReviewFAQSubmit
LIBRARIANS
TestimonialsSubscriptionsAccessResourcesLibrary Advisory BoardFAQ
RESEARCH
JoVE JournalMethods CollectionsJoVE Encyclopedia of ExperimentsArchive
EDUCATION
JoVE CoreJoVE BusinessJoVE Science EducationJoVE Lab ManualFaculty Resource CenterFaculty Site
Terms & Conditions of Use
Privacy Policy
Policies

Related Experiment Videos

Through-shell alkyllithium additions and borane reductions.

Ralf Warmuth1, Emily F Maverick, Carolyn B Knobler

  • 1Department of Chemistry, Kansas State University, Manhattan, Kansas 66506-3701, USA. warmuth@ksu.edu

The Journal of Organic Chemistry
|March 15, 2003
PubMed
Summary
This summary is machine-generated.

Related Concept Videos

You might also read

Related Articles

Articles linked to this work by shared authors, journal, and citation graph.

Sort by
Same author

p<i>K</i><sub>a</sub> Matching Enables Quantum Proton Delocalization in Acid-1-Methylimidazole Binary Mixtures.

Journal of chemical information and modeling·2025
Same author

Throwing in a Monkey Wrench to Test and Determine Geared Motion in the Dynamics of a Crystalline One-Dimensional (1D) Columnar Rotor Array.

Journal of the American Chemical Society·2019
Same author

Adaptation of the Barton Reaction to Carborane Chemistry: The Synthesis and Reactivity of 2-Hydroxyimino-1-hydroxymethylnona-B-methyl-1,12-dicarba-closo-dodecaborane(12).

Angewandte Chemie (International ed. in English)·2018
Same author

Modular Self-Assembly of a Microporous Solid Based upon Mercuracarborand-4 and a New Bonding Motif.

Angewandte Chemie (International ed. in English)·2018
Same author

Assembly of water-soluble, dynamic, covalent container molecules and their application in the room-temperature stabilization of protoadamantene.

Chemistry (Weinheim an der Bergstrasse, Germany)·2012
Same author

Benz[cd]indol-2(1H)-one at 298 and 100 K.

Acta crystallographica. Section C, Crystal structure communications·2012
Same journal

Tunable Palladium-Catalyzed [2π + 2σ] Cycloaddition/Alder-Ene Reactions of Vinylbicyclo[1.1.0]butanes with Cyclic <i>N</i>-Sulfonylimines.

The Journal of organic chemistry·2026
Same journal

Engineering a Carboxylesterase for Enantioselective Acyl Transfer Reaction.

The Journal of organic chemistry·2026
Same journal

Visible-Light-Promoted Trifluoromethylation/Ring-Opening Reaction of Vinylcyclopropanes by an EDA Complex.

The Journal of organic chemistry·2026
Same journal

Controlling Chemical Dynamics of Molecular Assemblies through Nanoconfinement: <i>o</i>-Nitrosocumene@Pd Nanocage.

The Journal of organic chemistry·2026
Same journal

Solvent Stabilization of Protic Oxonium/Ammonium Intermediates in Cation Radical Cyclization Reactions Investigated via Computational Approaches.

The Journal of organic chemistry·2026
Same journal

Concise Synthesis of Pyrano/Benzopyrano[2,3-<i>c</i>]pyrazol-6-ones via Ir/Rh-Catalyzed C-H Activation and Tandem Annulation.

The Journal of organic chemistry·2026
See all related articles

Researchers studied reactions of benzaldehyde, benzocyclobutenone, and benzocyclobutenedione inside a hemicarcerand. The incarcerated molecules underwent reduction and methylation, with reactivity influenced by their position within the host. Host-guest interactions also led to selective bond cleavage.

Area of Science:

  • Supramolecular Chemistry
  • Organic Synthesis
  • Host-Guest Chemistry

Background:

  • Hemicarcerands are unique host molecules capable of encapsulating guest molecules.
  • Understanding the reactivity of encapsulated guests is crucial for developing novel synthetic methodologies.
  • The confinement within a host can significantly alter the chemical behavior of guest molecules.

Purpose of the Study:

  • To investigate the borane reduction and methyllithium addition reactions of specific carbonyl compounds (benzaldehyde, benzocyclobutenone, benzocyclobutenedione) confined within a hemicarcerand.
  • To determine how the hemicarcerand host influences the reactivity and selectivity of these reactions.
  • To explore the potential for host-guest interactions to induce host molecule scission reactions.

Main Methods:

Related Experiment Videos

  • Synthesis and characterization of hemicarcerand-guest complexes.
  • Spectroscopic analysis (NMR) to determine guest orientation and host-induced shifts.
  • X-ray crystallography to elucidate the structural basis of host-guest interactions.
  • Molecular mechanics calculations to model preferred guest orientations.
  • Chemical reactions (borane reduction, organolithium addition) under controlled conditions.

Main Results:

  • All encapsulated guests underwent reduction and methylation.
  • Selective monoreduction and monomethylation were observed for benzocyclobutenedione.
  • Reactivity order for methyllithium addition: benzaldehyde < benzocyclobutenone << benzocyclobutenedione.
  • Reactivity order for borane reduction: benzaldehyde << benzocyclobutenone ≈ benzocyclobutenedione.
  • Elevated temperatures induced selective cleavage of the hemicarcerand's spanner or tetramethylenedioxy bridges.
  • Lithium alcoholates formed in situ exhibited enhanced basicity and nucleophilicity.

Conclusions:

  • The reactivity of incarcerated guests is strongly influenced by their orientation and location within the hemicarcerand.
  • Hemicarcerand confinement can lead to unique selectivity in organic reactions.
  • The enhanced basicity/nucleophilicity of intermediates within the host can trigger host molecule degradation.
  • This study highlights the potential of supramolecular hosts to control chemical reactivity and enable novel transformations.