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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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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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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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The Diels–Alder reaction is one of the robust methods for synthesizing unsaturated six-membered rings. The reaction involves a concerted cyclic movement of six π electrons: four π electrons from the diene and two π electrons from the dienophile.
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A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
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Elimination reactions of alkyl halides can yield one or more alkenes depending on the specific regiochemical and stereochemical considerations. While the regiochemistry of the reaction governs the location of the double bond in the product, the stereochemical requirements often influence the geometry.
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Stereospecific 3-Aza-Cope Rearrangement Interrupted Asymmetric Allylic Substitution-Isomerization.

Hong-Feng Zhuang1, Jun Gu1, Zhiwen Ye1

  • 1School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing, 210094, China.

Angewandte Chemie (International Ed. in English)
|October 17, 2024
PubMed
Summary

This study introduces an interrupted asymmetric allylic substitution-isomerization (Int-AASI) method for challenging asymmetric allylic arylation. The novel strategy efficiently produces enantioenriched products and axially chiral alkenes with high selectivity.

Keywords:
3-Aza-Cope RearrangementAsymmetric Allylic ArylationAsymmetric Allylic Substitution-IsomerizationAxially Chiral Alkenes

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Area of Science:

  • Organic Chemistry
  • Catalysis
  • Stereoselective Synthesis

Background:

  • Asymmetric allylic substitution is established for alkyl/heteroaryl nucleophiles.
  • Asymmetric allylic arylation of internal alkenes is underdeveloped.

Purpose of the Study:

  • To develop a method for asymmetric allylic arylation of acyclic internal alkenes.
  • To achieve high enantioselectivities for both allylic arylation products and axially chiral alkenes.

Main Methods:

  • A stepwise strategy involving a stereospecific 3-aza-Cope rearrangement interrupted asymmetric allylic substitution-isomerization (Int-AASI).
  • Experimental studies and Density Functional Theory (DFT) calculations to elucidate the mechanism and selectivity.

Main Results:

  • Successfully enabled asymmetric allylic arylation of acyclic internal alkenes.
  • Obtained enantioenriched allylic arylation products and axially chiral alkenes in high enantioselectivities.
  • Mechanism confirmed to involve asymmetric allylic amination, 3-aza-Cope rearrangement, and alkene isomerization.

Conclusions:

  • The Int-AASI strategy provides a viable route for challenging asymmetric allylic arylation.
  • High chemo-, regio-, stereo-, and stereospecificity were achieved and explained by DFT studies.