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Dichlorocarbene Addition to

van Eis MJ1, van Der Linde BS, de Kanter FJ

  • 1Scheikundig Laboratorium, Vrije Universiteit, De Boelelaan 1083, NL-1081 HV Amsterdam, The Netherlands.

The Journal of Organic Chemistry
|July 13, 2000
PubMed
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Dichlorocarbene reacts with [5]metacyclophane via a 1,2-addition, leading to a norcaradiene intermediate. This rearranges through chlorine migration, forming a bridged cycloheptatriene as the primary observable product.

Area of Science:

  • Organic Chemistry
  • Reaction Mechanisms
  • Computational Chemistry

Background:

  • Metacyclophanes are strained aromatic systems.
  • Carbene additions to strained systems exhibit unique reactivity.
  • Understanding reaction pathways is crucial for synthetic chemistry.

Purpose of the Study:

  • To investigate the reaction of dichlorocarbene with [5]metacyclophane.
  • To elucidate the mechanism of rearrangement and isomerization products.
  • To compare the migratory behavior in bridged versus flat systems.

Main Methods:

  • Experimental reaction of [5]metacyclophane with dichlorocarbene.
  • Spectroscopic characterization of reaction products.
  • Computational study (DFT) of reaction pathways and transition states.

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Main Results:

  • Dichlorocarbene undergoes 1,2-addition to the strained double bond of [5]metacyclophane.
  • The initial norcaradiene rearranges to a bridged cycloheptatriene.
  • A [1,5] sigmatropic chlorine migration forms the observable product 13b, with a calculated activation barrier of 70.2 kJ/mol.
  • Isomerization to 15b occurs via a dissociative mechanism.
  • Computational analysis indicates a concerted, slightly charge-separated pathway for the chlorine migration in the bridged system.

Conclusions:

  • The reaction pathway is distinct from phosphinidene complex addition.
  • Bridged cycloheptatrienes exhibit unique chlorine migration mechanisms compared to flat analogs.
  • Computational chemistry provides insights into the transition state of the chlorine migration.