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π Molecular Orbitals of the Allyl Cation and Anion01:18

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An allyl group is a three-carbon conjugated system where the sp³-hybridized allylic carbon is bonded to a CH=CH2 group via a single bond. Allyl anions can be obtained by treating propene with a strong base that can deprotonate methyl groups. Allyl cations are formed as intermediates during substitution reactions involving allylic halides. In both cases, the hybridization of the allylic carbon changes from sp3 to sp2, giving rise to a carbon chain with three sp2-hybridized carbons, each with...
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π Molecular Orbitals of the Allyl Radical01:27

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Allyl radicals are three-carbon conjugated systems. They are readily formed as intermediates in halogenation reactions of alkenes involving the addition of halogen to the allylic carbon instead of the double bond. As seen in allyl cations and anions, each of the three sp2-hybridized carbon atoms in allyl radicals has an unhybridized p orbital. These orbitals combine to give three π molecular orbitals.
The allyl systems have identical molecular orbitals but differ in the number of π electrons....
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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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Introduction
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
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Typically, when alkenes react with halogens at low temperatures, an addition reaction occurs. However, upon increasing the temperature or under reaction conditions that form radicals, providing a low but steady concentration of halogen radicals, allylic substitution reaction is favored. This is because allylic hydrogens are very reactive as the formed intermediate is resonance stabilized. For example, when propene is treated with chlorine in the gas phase at 400 °C, it undergoes allylic...
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Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation02:24

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Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
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Allylic C-H functionalization via group 9 π-allyl intermediates.

Taylor A F Nelson1, Michael R Hollerbach1, Simon B Blakey1

  • 1Department of Chemistry, Emory University, Atlanta, Georgia 30322, USA. sblakey@emory.edu.

Dalton Transactions (Cambridge, England : 2003)
|September 10, 2020
PubMed
Summary

Group 9 Cp* transition-metal complexes enable versatile allylic C-H functionalization, expanding reaction scope to diverse olefins and coupling partners via MCp*-π-allyl intermediates. This overview details recent advances and remaining limitations in catalytic C-N, C-O, and C-C bond formation.

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Area of Science:

  • Organometallic Chemistry
  • Catalysis
  • Organic Synthesis

Background:

  • Allylic C-H functionalization is crucial for synthesizing complex organic molecules.
  • Group 9 Cp* transition-metal complexes have emerged as powerful catalysts in this field.
  • Previous methods were limited in substrate scope and reaction diversity.

Purpose of the Study:

  • To provide a mechanistic overview of allylic C-H functionalization catalyzed by group 9 Cp* transition-metal complexes.
  • To highlight recent advances and applications of these catalytic systems.
  • To identify current limitations and future directions in the field.

Main Methods:

  • Review of literature on catalytic allylic C-H functionalization.
  • Mechanistic analysis of reactions proceeding via MCp*-π-allyl intermediates.
  • Categorization of reactions based on mechanistic paradigms.

Main Results:

  • Demonstrated expansion of allylic C-H functionalization to di- and trisubstituted olefins.
  • Reported successful catalytic C-N, C-O, and C-C bond formations.
  • Illustrated the role of MCp*-π-allyl intermediates in these transformations.

Conclusions:

  • Group 9 Cp* transition-metal complexes offer a versatile platform for allylic C-H functionalization.
  • Significant progress has been made in broadening substrate scope and reaction types.
  • Further research is needed to overcome existing limitations and enhance catalytic efficiency.