Coupling reaction

Source: Wikipedia, the free encyclopedia.

In

cross coupling reaction.[1][2][3]

palladium-catalyzed cross coupling reactions.[4][5]

Broadly speaking, two types of coupling reactions are recognized:

Homo-coupling types

Coupling reactions are illustrated by the Ullmann reaction:

Ullmann overview
Ullmann overview
Reaction Year Organic compound Coupler Remark
Wurtz reaction 1855 R-X sp3 Na as reductant dry ether as medium
Pinacol coupling reaction 1859 R-HC=O or R2(C=O) various metals requires proton donor
Glaser coupling 1869 RC≡CH sp Cu O2 as H-acceptor
Ullmann reaction 1901 Ar-X sp2 Cu high temperatures
Fittig reaction Ar-X sp2 Na dry ether as medium
Scholl reaction 1910 ArH sp2 NaAlCl4(l) O2 as H-acceptor; presumably trace Fe3+ catalyst; requires high heat

Cross-coupling types

Main article: Cross-coupling reaction
The Heck reaction
The Heck reaction
Reaction Year Reactant A Reactant B Catalyst Remark
Grignard reaction 1900 R-MgBr sp, sp2, sp3 R-HC=O or R(C=O)R2 sp2 not catalytic
Gomberg-Bachmann reaction
 1924 Ar-H sp2 Ar'-N2+X− sp2 not catalytic
Cadiot-Chodkiewicz coupling
 1957 RC≡CH sp RC≡CX sp Cu requires base
Castro-Stephens coupling
 1963 RC≡CH sp Ar-X sp2 Cu
Corey-House synthesis
 1967 R2CuLi or RMgX sp3 R-X sp2, sp3 Cu Cu-catalyzed version by Kochi, 1971
Cassar reaction 1970 Alkene sp2 R-X sp3 Pd requires base
Kumada coupling 1972 Ar-MgBr sp2, sp3 Ar-X sp2 Pd or Ni or Fe
Heck reaction 1972 alkene sp2 Ar-X sp2 Pd or Ni requires base
Sonogashira coupling 1975 RC≡CH sp R-X sp3 sp2 Pd and Cu requires base
Murahashi coupling[7] 1975 RLi sp2, sp3 Ar-X sp2 Pd or Ni Pd-catalyzed version by Murahashi, 1979
Negishi coupling 1977 R-Zn-X sp3, sp2, sp R-X sp3 sp2 Pd or Ni
Stille cross coupling
 1978 R-SnR3 sp3, sp2, sp R-X sp3 sp2 Pd
Suzuki reaction 1979 R-B(OR)2 sp2 R-X sp3 sp2 Pd or Ni requires base
Hiyama coupling 1988 R-SiR3 sp2 R-X sp3 sp2 Pd requires base
Buchwald-Hartwig reaction
 1994 R2N-H sp3 R-X sp2 Pd N-C coupling,
second generation free amine
Fukuyama coupling 1998 R-Zn-I sp3 RCO(SEt) sp2 Pd or Ni[8]
Liebeskind–Srogl coupling 2000 R-B(OR)2 sp3, sp2 RCO(SEt) Ar-SMe sp2 Pd requires
CuTC
(Li) Cross dehydrogenative coupling(CDC) 2004 R-H sp, sp2, sp3 R'-H sp, sp2, sp3 Cu, Fe, Pd etc requires oxidant or dehydrogenation
Wurtz-Fittig reaction R-X sp3 Ar-X sp2 Na dry ether

Applications

Coupling reactions are routinely employed in the preparation of pharmaceuticals.[3] Conjugated polymers are prepared using this technology as well.[9]

References

  1. ISBN 978-1-84127-107-1
  2. ISBN 978-1-84973-896-5
  3. ^
    ISBN 978-3-540-01603-8
    .
  4. ^ "The Nobel Prize in Chemistry 2010 - Richard F. Heck, Ei-ichi Negishi, Akira Suzuki". NobelPrize.org. 2010-10-06. Retrieved 2010-10-06.
  5. PMID 22573393
    .
  6. ISBN 978-0-471-72091-1
  7. S2CID 244613990
    .
  8. PMID 23961769
    .
  9. ISBN 978-1-891389-53-5
    .
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