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Suzuki reaction

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The Suzuki reaction is the organic reaction of an aryl- or vinyl-boronic acid with an aryl- or vinyl-halide catalyzed by a palladium(0) complex,[1][2][3] which can also be in the form of a nanomaterial-based catalyst. It is widely used to synthesize poly-olefins, styrenes, and substituted biphenyls, and has been extended to incorporate alkyl bromides.[4] Several reviews have been published.[5][6][7]

The Suzuki reaction
The Suzuki reaction

The reaction also works with pseudohalides, such as triflates (OTf), instead of halides. Boronic esters and organotrifluoroborate salts may be used instead of boronic acids.

Relative reactivity: R2-I > R2-OTf > R2-Br >> R2-Cl

First published in 1979 by Akira Suzuki, the Suzuki reaction couples boronic acids (containing an organic substituent) to halides. The reaction relies on a palladium catalyst such as tetrakis(triphenylphosphine)palladium(0) to effect part of the transformation. The palladium catalyst (more strictly a pre-catalyst) is 4-coordinate, and usually involves phosphine supporting groups.

The 2010 Nobel Prize in Chemistry was awarded in part to Suzuki for his discovery and development of this reaction. In many publications this reaction also goes by the name Suzuki-Miyaura reaction. It is also often referred to as "Suzuki Coupling".

Reaction mechanism

The mechanism of the Suzuki reaction is best viewed from the perspective of the palladium catalyst. The first step is the oxidative addition of palladium to the halide 2 to form the organopalladium species 3. Reaction with base gives intermediate 4, which via transmetalation[8] with the boron-ate complex 6 forms the organopalladium species 8. Reductive elimination of the desired product 9 restores the original palladium catalyst 1.

The mechanism of the Suzuki reaction
The mechanism of the Suzuki reaction

Oxidative addition

Oxidative addition proceeds with retention of stereochemistry with vinyl halides, while giving inversion of stereochemistry with allylic and benzylic halides.[9] The oxidative addition initially forms the cis-palladium complex, which rapidly isomerizes to the trans-complex.[10]

Reductive elimination

Using deuterium-labelling, Ridgway et al. have shown the reductive elimination proceeds with retention of stereochemistry.[11] Relative reactivity of different metal complexes in the C-C reductive elimination was established: Pd(IV), Pd(II) > Pt(IV), Pt(II), Rh(III) > Ir(III), Ru(II), Os(II).[12]

Scope

The Suzuki coupling has been frequently used in syntheses of complex compounds.[13] The Suzuki coupling has been used on a citronellal derivative for the synthesis of caparratriene, a natural product that is highly active against leukemia:[14]

Synthesis of caparratriene using the Suzuki coupling
Synthesis of caparratriene using the Suzuki coupling

Recent applications of the Suzuki–Miyaura cross-coupling reaction in organic synthesis have been summarized by Kotha and co-workers.[15] With a novel organophosphine ligand (SPhos), a catalyst loading of down to 0.001 mol% has been reported[16]:

Suzuki Reaction Catalyst Loading Barder 2005
Suzuki Reaction Catalyst Loading Barder 2005

See also

References

  1. ^ Miyaura, Norio; Yamada, Kinji ; Suzuki, Akira (1979). "A new stereospecific cross-coupling by the palladium-catalyzed reaction of 1-alkenylboranes with 1-alkenyl or 1-alkynyl halides". Tetrahedron Letters. 20 (36): 3437–3440. doi:10.1016/S0040-4039(01)95429-2.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  2. ^ Miyaura, Norio; Suzuki, Akira (1979). "Stereoselective synthesis of arylated (E)-alkenes by the reaction of alk-1-enylboranes with aryl halides in the presence of palladium catalyst". Chem. Comm. (19): 866–867. doi:10.1039/C39790000866.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  3. ^ Miyaura, Norio; Suzuki, Akira (1995). "Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds". Chemical Reviews. 95 (7): 2457–2483. doi:10.1021/cr00039a007.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  4. ^ http://pubs.acs.org/cgi-bin/abstract.cgi/jacsat/2002/124/i46/abs/ja0283899.html
  5. ^ Suzuki, A. Pure Appl. Chem. 1991, 63, 419-422. (Review)
  6. ^ Miyaura, Norio; Suzuki, Akira (1979). "Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds". Chemical reviews. 95 (7): 2457–2483. doi:10.1021/cr00039a007.{{cite journal}}: CS1 maint: multiple names: authors list (link)(Review)
  7. ^ Suzuki, A. J. Organometallic Chem. 1999, 576, 147–168. (Review)
  8. ^ Matos, K.; Soderquist, J. A. J. Org. Chem. 1998, 63, 461–470. (doi:10.1021/jo971681s)
  9. ^ Stille, J. K.; Lau, K. S. Y. Acc. Chem. Res. 1977, 10, 434–442. (doi:10.1021/ar50120a002)
  10. ^ Casado, A. L.; Espinet, P. Organometallics 1998, 17, 954–959.
  11. ^ Ridgway, B. H.; Woerpel, K. A. J. Org. Chem. 1998, 63, 458–460. (doi:10.1021/jo970803d)
  12. ^ (a) J. Am. Chem. Soc., 2002, 124 (11), 2839; doi:10.1021/ja017476i. (b) Organometallics, 2005, 24, 715. doi:10.1021/om0490841
  13. ^ (a) A. Balog, D. Meng, T. Kamenecka, P. Bertinato, D.-S. Su, E.J. Sorensen and S.J. Danishefsky, "Total Synthesis of (–)-Epothilone A" Angew. Chem., Int. Ed. Engl., 1996, 35, 2801. doi:10.1002/anie.199628011 (b) J. Liu, S. D. Lotesta and E. J. Sorensen, "A concise synthesis of the molecular framework of pleuromutilin", Chem. Commun., 2011, 47, 1500. doi:10.1039/C0CC04077K
  14. ^ Vyvyan, J.R. (1999). "An expedient total synthesis of (+/-)-caparratriene". Tetrahedron Letters. 40 (27): 4947–4949. doi:10.1016/S0040-4039(99)00865-5. Retrieved 2008-01-02.
  15. ^ Recent applications of the Suzuki–Miyaura cross-coupling reaction in organic synthesis Sambasivarao Kotha, Kakali Lahiri and Dhurke Kashinath Tetrahedron 2002, 48, 9633-9695 doi:10.1016/S0040-4020(02)01188-2
  16. ^ Catalysts for Suzuki-Miyaura Coupling Processes: Scope and Studies of the Effect of Ligand Structure Timothy E. Barder, Shawn D. Walker, Joseph R. Martinelli, and Stephen L. Buchwald J. AM. CHEM. SOC. 2005, 127, 4685-4696 doi:10.1021/ja042491j
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