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Copper: Organometallic Chemistry

  1. Bruce H. Lipshutz,
  2. Steven S. Pfeiffer

Published Online: 15 DEC 2011

DOI: 10.1002/9781119951438.eibc0051

Encyclopedia of Inorganic and Bioinorganic Chemistry

Encyclopedia of Inorganic and Bioinorganic Chemistry

How to Cite

Lipshutz, B. H. and Pfeiffer, S. S. 2011. Copper: Organometallic Chemistry . Encyclopedia of Inorganic and Bioinorganic Chemistry. .

Author Information

  1. University of California, Santa Barbara, CA, USA

Publication History

  1. Published Online: 15 DEC 2011

Abstract

Much of copper chemistry over the past decade has transitioned toward catalysis, driven in large measure by environmental rather than economic concerns. Catalytic processes have appeared in large numbers, in particular due to the advances made in both the design of new ligands that effectively coordinate copper, but also due to their increased availability. Applications of copper-catalyzed processes to bond formations have gone well-beyond those of a C[BOND]C nature, nowadays including C[BOND]N, C[BOND]O, C[BOND]S, C[BOND]P, and C[BOND]H types. Asymmetric variants based on nonracemically ligated copper salts and copper hydride have led to highly valued entries to chiral products of great use in synthesis. Transmetalations from various metals (e.g. Zn, Zr, etc.) to copper also continue to play a vital role in organic synthesis, and are discussed herein as well.

Considerable progress on many physical organic fronts relating to copper chemistry has been made. New advances in technologies that shed light on structural aspects of copper reagents are now available (extended X-ray absorption fine structure, EXAFS, X-ray absorption near edge structure, XANES) and are being used to accompany X-ray analyses and highly sophisticated NMR techniques. High-level computer calculations have led to theoretical ‘pictures’ illustrating the mechanistic pathways that may be followed by some of the most commonly used reactions in copper chemistry (e.g. 1,4-additions). Taken in their entirety, these developments suggest that this past decade has been a most productive period in the continuing evolution of copper chemistry.

Keywords:

  • allylic alkylation;
  • carbocupration;
  • conjugate addition;
  • ligand;
  • metallocarbene;
  • organocuprate;
  • Schiff's base;
  • transmetalation