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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.
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Thermal Sigmatropic Reactions: Overview01:16

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Sigmatropic rearrangements are a class of pericyclic reactions in which a σ bond migrates from one part of a π system to another. These are intramolecular rearrangements where the total number of σ and π bonds remain unchanged.
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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.
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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.
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Prochirality

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The concept of prochirality leads to the nomenclature of the individual faces of a molecule and plays a crucial role in the enantioselective reaction. It is a concept where two or more achiral molecules react to produce chiral products. A typical process is the reaction of an achiral ketone to generate a chiral alcohol. Here, the achiral reactant reacts with an achiral reducing agent, sodium borohydride, to generate an equimolar mixture of the chiral enantiomers of the product. For example, an...
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In an SN2 reaction, the nucleophilic attack on the substrate and departure of the leaving group occurs simultaneously through a transition state. As the nucleophile approaches the substrate from the back-side, the configuration of the substrate carbon changes from tetrahedral to trigonal bipyramidal and then back to tetrahedral, leading to an inversion in the configuration of the product.
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[2,3]-Sigmatropic rearrangement with [1.1.1]propellane.

Suparnak Midya1, Aksar Ali1, Durga Prasad Hari2

  • 1Department of Organic Chemistry, Indian Institute of Science, Bangalore, India.

Nature Communications
|July 7, 2025
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Summary

[1.1.1]propellane serves as a carbene precursor for a novel [2,3]-sigmatropic rearrangement, efficiently forming allenylated or allylated methylenecyclobutanes. This method also enables synthesis of bicyclo[2.1.1]hexanes, valuable benzene bioisosteres.

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Area of Science:

  • Organic Chemistry
  • Synthetic Methodology
  • Carbene Chemistry

Background:

  • Established [1.1.1]propellane reactivity involves addition reactions at the bridge C-C bond.
  • Formation of bicyclo[1.1.1]pentane derivatives is a known outcome.
  • Limited methods exist for utilizing [1.1.1]propellane as a carbene precursor.

Purpose of the Study:

  • To develop a novel [2,3]-sigmatropic rearrangement using [1.1.1]propellane.
  • To access allenylated or allylated methylenecyclobutanes.
  • To explore subsequent applications in synthesizing substituted bicyclo[2.1.1]hexanes.

Main Methods:

  • [2,3]-sigmatropic rearrangement of [1.1.1]propellane with propargyl and allyl sulfides/selenides.
  • Photocatalyzed radical cascade cyclization for bicyclo[2.1.1]hexane synthesis.
  • Density functional theory (DFT) calculations to elucidate reaction mechanism.

Main Results:

  • Efficient and scalable synthesis of allenylated/allylated methylenecyclobutanes.
  • Reaction proceeds under mild conditions with broad functional group tolerance.
  • Successful synthesis of substituted bicyclo[2.1.1]hexanes, potential benzene bioisosteres.
  • DFT calculations indicate a copper-bound five-membered transition state.

Conclusions:

  • A new synthetic route utilizing [1.1.1]propellane as a carbene precursor has been established.
  • The method provides access to valuable methylenecyclobutane and bicyclo[2.1.1]hexane scaffolds.
  • The developed bicyclo[2.1.1]hexane derivatives are promising bioisosteres for drug discovery.