Jove
Visualize
Contact Us

Related Experiment Videos

Structure-nucleophilicity relationships for enamines.

Bernhard Kempf1, Nathalie Hampel, Armin R Ofial

  • 1Department Chemie der Ludwig-Maximilians-Universität München, Butenandtstrasse 5-13 (Haus F) 81377 München, Germany.

Chemistry (Weinheim an Der Bergstrasse, Germany)
|May 29, 2003
PubMed
Summary

This study quantifies the nucleophilic reactivity of enamines, pyrroles, and indoles using benzhydryl cations. Enamine reactivity spans ten orders of magnitude, comparable to enol ethers and carbanions.

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

Quantifying the enamine-type nucleophilic reactivity of α-aryl vinyl azides.

Chemical communications (Cambridge, England)·2026
Same author

From Oxygen to Tellurium: The Impact of the Chalcogen on Nucleophilicities and Basicities of Isochalcogenourea Catalysts.

Angewandte Chemie (International ed. in English)·2025
Same author

Revisiting Mayr's reactivity database: expansion, sensitivity analysis, and uncertainty quantification.

Organic & biomolecular chemistry·2025
Same author

Reactivity of δ-Functionalized Para-Quinone Methides in Nucleophilic Addition Reactions.

Chemistry (Weinheim an der Bergstrasse, Germany)·2025
Same author

Synthesis of Nucleoside Derivatives by Biomimetic Ester Migration.

Chembiochem : a European journal of chemical biology·2025
Same author

Pyridinamide Ion Pairs: Design Principles for Super-Nucleophiles in Apolar Organic Solvents.

The Journal of organic chemistry·2025
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

Area of Science:

  • Organic Chemistry
  • Physical Chemistry

Background:

  • Electron-rich pi-systems like enamines are crucial nucleophiles in organic synthesis.
  • Understanding their reactivity is key to controlling reaction outcomes and designing new synthetic pathways.

Purpose of the Study:

  • To investigate the reaction kinetics of benzhydryl cations with a diverse range of enamines, pyrroles, and indoles.
  • To determine the nucleophilicity (N) and slope (s) parameters for these electron-rich pi-systems.
  • To compare the reactivity of enamines with other nucleophiles like enol ethers and carbanions.

Main Methods:

  • Photometric investigation of reaction kinetics in dichloromethane.
  • Application of the equation log k (20 °C) = s(E+N) to derive nucleophilicity and slope parameters.
  • Measurement of equilibrium constants for iminium ion formation in select cases.

Related Experiment Videos

Main Results:

  • The nucleophilic reactivities of 22 enamines, three pyrroles, and three indoles were systematically quantified.
  • Enamine nucleophilicity was found to span over ten orders of magnitude.
  • Reactivity was compared to silyl enol ethers, silyl ketene acetals, and carbanions, revealing a broad spectrum of reactivity.

Conclusions:

  • Enamines exhibit a wide range of nucleophilic reactivity, bridging the gap between less reactive enol ethers and highly reactive carbanions.
  • The derived kinetic parameters provide valuable insights into the behavior of these electron-rich pi-systems.
  • Rate constants primarily reflect carbon-carbon bond formation due to thermodynamic considerations of N-attack products.