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Cross-Coupling with Organosilicon Compounds

  1. Wen-Tau T. Chang,
  2. Russell C. Smith,
  3. Christopher S. Regens,
  4. Aaron D. Bailey,
  5. Nathan S. Werner,
  6. Scott E. Denmark

Published Online: 16 DEC 2011

DOI: 10.1002/0471264180.or075.03

Organic Reactions

Organic Reactions

How to Cite

Chang, W.-T. T., Smith, R. C., Regens, C. S., Bailey, A. D., Werner, N. S. and Denmark, S. E. 2011. Cross-Coupling with Organosilicon Compounds. Organic Reactions. 213–746.

Author Information

  1. University of Illinois, Department of Chemistry, Urbana, Illinois

Publication History

  1. Published Online: 16 DEC 2011

Abstract

Organosilicon functions possess many properties that make them ideal donors of organic groups in cross-coupling reactions. Through the addition of an appropriate silicophilic Lewis base, an in situ pentacoordinate silane can effectively transfer an organic group. This feature allows for the rapid development of silicon cross-coupling methods that continue today. Organosilicon-based cross-coupling has now become a practical, viable, and in some cases, superior compared with organoboron,-zinc,-tin couplings. The unique properties of organosilicon compounds provide a number of distinct advantages to their use as donors in transition-metal catalyzed cross-coupling reactions: 1, silicon moieties can be introduced into organic substrates by many general and high-yielding methods for the construction of silicon carbon bonds; 2, organosilicon reagents are chemically robust and allow isolation and purification of products and are compatible with many functional groups; 3, silicon-containing by-products of the coupling are of low molecular weight, are nontoxic, and are easily removed from the reaction mixture; 4, a number of mild methods are available.

This chapter presents a thorough overview of the various combinations of transferable groups and organic electrophiles. The scope is limited to the combination of silicon-bearing nucleophiles with halo or related electrophiles under catalysis by palladium or nickel complexes wherein the silyl halide is lost.

Keywords:

  • Cross coupling;
  • Organosilicon compounds;
  • Alkenylsilanes;
  • Allylsilanes;
  • Benzylsilanes;
  • Halosilanes;
  • Silanols;
  • Silanolates;
  • Alkoxysilanes;
  • Polysiloxanes;
  • Disiloxanes;
  • Cyclic silyl ethers;
  • Ruthenium catalysts;
  • Palladium;
  • Ligands;
  • Solvents;
  • Fluoride;
  • Mechanisms;
  • Enantioselectivity;
  • Experimental procedures