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Related Concept Videos

Carbocations02:10

Carbocations

Carbocations are one of the reaction intermediates formed during several nucleophilic substitutions or elimination reactions. A carbocation is an electron-deficient species with the central carbon atom having six electrons and three bonded atoms. The central carbon in a carbocation is sp2 hybridized with trigonal planar geometry. It has an empty p orbital perpendicular to the plane of the structure that can accept electrons. Thus, carbocations act as strong electrophiles and may react with any...
Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration02:34

Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration

The rate of acid-catalyzed hydration of alkenes depends on the alkene's structure, as the presence of alkyl substituents at the double bond can significantly influence the rate.
[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement01:21

[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement

The Cope rearrangement is classified as a [3,3] sigmatropic shift in 1,5-dienes, leading to a more stable, isomeric 1,5-diene. The reaction involves a concerted movement of six electrons, four from two π bonds and two from a σ bond, via an energetically favorable chair-like transition state.
[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement01:24

[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement

The Claisen rearrangement is a [3,3] sigmatropic rearrangement of allyl vinyl ethers to unsaturated carbonyl compounds. The rearrangement is a concerted pericyclic reaction proceeding via a chair-like transition state.
Preparation of Diols and Pinacol Rearrangement01:57

Preparation of Diols and Pinacol Rearrangement

Compounds bearing two hydroxyl groups are known as diols. When the hydroxyl groups are located on adjacent carbon atoms, the diols are called vicinal diols or glycols. Under acidic conditions, vicinal diols undergo a specific reaction called pinacol rearrangement.
The reaction begins with transferring a proton from the acid catalyst to one of the hydroxyl groups, producing an oxonium ion.
Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule02:17

Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule

If a set of reactants can yield multiple constitutional isomers, but one of the isomers is obtained as the major product, the reaction is said to be regioselective. In such reactions, bond formation or breaking is favored at one reaction site over others.
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...

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Updated: May 13, 2026

Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
10:44

Isolating Free Carbenes, their Mixed Dimers and Organic Radicals

Published on: April 19, 2019

Caryolene-forming carbocation rearrangements.

Quynh Nhu N Nguyen1, Dean J Tantillo

  • 1Department of Chemistry, University of California-Davis, 1 Shields Avenue, Davis, CA 95616, USA.

Beilstein Journal of Organic Chemistry
|March 19, 2013
PubMed
Summary
This summary is machine-generated.

Density functional theory reveals two mechanisms for caryolene formation, a precursor to caryol-1(11)-en-10-ol. Both involve cycloadditions, with one pathway featuring a base-catalyzed sequence and the other intramolecular proton transfer.

Keywords:
carbocationcycloadditiondensity functional theorymechanismreactive intermediatesterpene

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Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes
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Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes

Published on: September 8, 2013

Area of Science:

  • Organic Chemistry
  • Computational Chemistry
  • Biochemistry

Background:

  • Caryolene is a potential biosynthetic precursor to caryol-1(11)-en-10-ol.
  • Understanding caryolene formation mechanisms is crucial for elucidating terpene biosynthesis pathways.

Purpose of the Study:

  • To investigate and elucidate the detailed mechanisms of caryolene formation using computational methods.
  • To compare the energetic feasibility of different proposed pathways for caryolene synthesis.

Main Methods:

  • Density functional theory (DFT) calculations were employed to model reaction pathways.
  • Analysis of transition states, intermediates, and energy barriers for proposed mechanisms.

Main Results:

  • Two distinct mechanisms for caryolene formation were identified and characterized.
  • Mechanism 1 involves base-catalyzed deprotonation/reprotonation with a tertiary carbocation.
  • Mechanism 2, with a higher energy barrier, involves intramolecular proton transfer and secondary carbocation/hydrogen-bridged intermediates.

Conclusions:

  • Both identified mechanisms proceed via concerted suprafacial/suprafacial [2 + 2] cycloadditions.
  • The asynchronicity of these cycloadditions circumvents orbital symmetry constraints, enabling the reactions.
  • These findings provide computational insights into the biosynthesis of caryolene and related compounds.