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Transition metals are defined as those elements that have partially filled d orbitals. As shown in Figure 1, the d-block elements in groups 3–12 are transition elements. The f-block elements, also called inner transition metals (the lanthanides and actinides), also meet this criterion because the d orbital is partially occupied before the f orbitals.
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Peptide modification and cyclization via transition-metal catalysis.

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Transition-metal catalysis enables novel peptide modifications and cyclizations using amino acid reactivity. Recent advances in couplings and C-H functionalizations expand peptide chemistry for drug discovery and materials science.

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Area of Science:

  • Organic Chemistry
  • Catalysis
  • Peptide Chemistry

Background:

  • Transition-metal catalysis offers powerful tools for modifying peptides.
  • Proteinogenic amino acids possess inherent reactivity amenable to catalytic functionalization.
  • Conventional peptide modification methods have limitations in scope and efficiency.

Purpose of the Study:

  • To review recent advances in transition-metal catalyzed peptide modification.
  • To highlight key developments in heteroatom couplings, decarboxylative cross-couplings, and C-H functionalizations.
  • To underscore the potential of these methods in drug discovery and materials science.

Main Methods:

  • Focus on transition-metal catalyzed reactions.
  • Review of literature on heteroatom couplings, decarboxylative cross-couplings, and C-H functionalizations of peptides.
  • Discussion of the application of these methods to proteinogenic amino acids.

Main Results:

  • Significant expansion of peptide modification and cyclization strategies.
  • Development of novel heteroatom couplings for peptides.
  • Advancements in decarboxylative cross-couplings and C-H functionalizations of amino acids.
  • Demonstration of access to complex peptide structures.

Conclusions:

  • Transition-metal catalysis has revolutionized peptide modification.
  • These advanced methods provide access to high-value peptide targets.
  • The reviewed strategies hold significant promise for drug discovery and materials science applications.