Categories: C-C Bond Formation > Arenes >

Olefination, Arylation

Name Reactions

Heck Reaction

Versatile Cross Coupling Methods: Hiyama Coupling (R-X + R'-SiR''3) Hiyama-Denmark Coupling (R-X + R-SiMe2OH) Kumada Coupling (R-X + R'-MgX) Negishi Coupling (R-X + R'-ZnX) Stille Coupling (R-X + R'-SnR''3) Suzuki Coupling (R-X + R'-BY3)

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Recent Literature

A general and mild protocol of oxygen-promoted Pd(II) catalysis allows a selective cross-couplings of alkenyl- and arylboron compounds with various olefins. Unlike most cross-coupling reactions, this new methodology works well even in the absence of bases, consequently averting undesired homo-couplings.
K. S. Yoo, C. H. Yoon, J. W. Jung, J. Am. Chem. Soc., 2006, 128, 16348-16393.

A mild and efficient Pd(II) catalysis leads to the formation of carbon-carbon bonds between various organoboron compounds and alkenes. The resultant Pd(0) species is reoxidized by molecular oxygen to Pd(II). This protocol promotes the desired Pd(II) catalysis, whereas the competing Pd(0) pathways (Heck or Suzuki) are retarded.
Y. C. Jung, R. K. Mishra, C. H. Yoon, K. W. Jung, Org. Lett., 2003, 5, 2231-2234.

The palladium-catalyzed cross-coupling reaction of potassium vinyltrifluoroborate with aryl electrophiles can generally be effected using 2 mol % of PdCl₂ and 6 mol % of PPh₃ as a catalyst system in THF/H₂O with Cs₂CO₃ as a base. Good yields are obtained in the presence of various functional groups.
G. A. Molander, A. R. Brown, J. Org. Chem., 2006, 71, 9681-9686.

A novel bis-phenanthryl N-heterocyclic carbene (NHC) based palladium acetate catalyst was effective for the coupling of various aryl and vinyl chlorides with organoboron compounds. Hindered tri- and tetra-ortho substituted products were efficiently produced. Benzyl chloride was also found to be a useful coupling partner and trimethylboroxine was used to give methylated products.
C. Song, Y. Ma, Q. Chai, C. Ma, W. Jiang, M. B. Andrus, Tetrahedron, 2005, 61, 7438-7446.

Efficient, stereospecific palladium(0)-catalyzed Suzuki-Miyaura cross-couplings of potassium aryl- and heteroaryltrifluoroborates with alkenyl bromides can generally be carried out using 2 mol % of palladium catalyst and 3 equiv of base in toluene/H₂O.
G. A. Molander, T. Fumagalli, J. Org. Chem., 2006, 71, 5743-5747.

Addition of arylmagnesium bromides to aryl(alkyl)acetylenes gave high yields of the corresponding alkenylmagnesium reagents in the presence of an iron catalyst and a N-heterocyclic carbene ligand. Subsequent treatment with electrophiles allows the formation of tetrasubstituted alkenes.
T. Yamagami, R. Shintani, E. Shirakawa, T. Hayashi, Org. Lett., 2007, 9, 1045-1048.

A mild, FeCl₃-catalyzed addition of electron-rich arenes to aryl-substituted alkynes gives 1,1-diaryl alkenes in good yields.
R. Li, S. R. Wang, W. Lu, Org. Lett., 2007, 9, 2219-2222.

Palladium-catalyzed cross-coupling reaction of 1,1-diboryl-1-alkenes with aryl and alkenyl iodides proceeded stereoselectively to the corresponding mono-coupled product as a single diastereomer. A subsequent coupling with another aryl iodide afforded various triarylalkenes in their stereochemically pure form.
M. Shimizu, C. Nakamaki, K. Shimono, M. Schelper, T. Kurahashi, T. Hiyama, J. Am. Chem. Soc., 2005, 127, 12506-12507.

Palladium-catalyzed Heck and Suzuki coupling reactions of arenediazonium salts were performed at room temperature, without added base, under aerobic conditions using a thiourea-based C₂-symmetric ligand. The reactions produced product in 4 h in good yield.
M. Dai, B. Liang, C. Wang, J. Chen, Z. Yang, Org. Lett., 2004, 6, 221-224.

The employment of hydrophobic ionic liquids dramatically enhanced the activity of metal triflates in Friedel-Crafts alkenylations of aromatic compounds with various alkyl- and aryl-substituted alkynes.
C. E. Song, D.-U. Jung, S. Y. Choung, E. J. Roh, S.-G. Lee, Angew. Chem., 2004, 116, 6309-6311.

A variety of organolithiums are added to terminal and 2,2-disubstituted epoxides in the presence of LTMP to generate alkenes in a completely regio- and highly stereoselective manner. Arylated alkenes, dienes, allylsilanes, and enynes are accessed using this procedure.
D. M. Hodgson, M. J. Fleming, S. J. Stanway, J. Org. Chem., 2007, 72, 4763-4773.

Cycloadditions of Diels-Alder dienophiles containing linked enyne sites, each substituted with activating groups, occurred specifically at the acetylenic center. A remote acrylyl group bound to the olefinic site totally dominated the regiochemical course of the cycloaddition. Explanations for these findings at the computational level are provided.
M. Dai, D. Sarlah, M. Yu, S. J. Danishefsky, G. O. Jones, K. N. Houk, J. Am. Chem. Soc., 2007, 129, 645-657.

Air-stable palladium complexes with phosphinous acid ligands serve as efficient catalysts for various cross-coupling reactions of vinyl and aryl chlorides with arylboronic acids, arylzinc reagents, and thiols.
G. Y. Li, J. Org. Chem., 2002, 67, 3643-3650.

Highly reactive zinc metal was readily prepared by electrolysis of a DMF solution containing naphthalene and a supporting electrolyte in a one-compartment cell fitted with a platinum cathode and a zinc anode. This reactive zinc was used for efficient transformation of ethyl 2-bromoacrylate into the corresponding organozinc compound, which was reacted with various aryl iodides in the presence of palladium catalyst to give ethyl 2-arylpropenoates in high yields.
A. A. Jalil, N. Kurono, M. Tokuda, Synthesis, 2002, 2681-2686.

4-Substituted 1,2-oxaborol-2(5H)-ols were prepared through copper-catalyzed carbomagnesation of propargyl alcohol, followed by the transmetallation of magnesium to boron in a one-pot procedure. The Suzuki-Miyaura cross-coupling of these new 2,2-disubstituted alkenylboronic acids with aryl halides afforded stereodefined 2,3-disubstituted allyl alcohols in good to excellent yields.
G.-H. Fang, Z.-J. Yan, M.-Z. Deng, Synthesis, 2006, 1148-1154.

N-Vinylpyridinium and -trialkylammonium tetrafluoroborate salts represent a new class of electrophilic coupling partner for Pd(0)-catalyzed Suzuki cross-coupling reactions with various boronic acids in high yields. The crystalline, air-stable, and nonhygroscopic salts are easily prepared from activated acetylenes and pyridinium or trialkylammonium tetrafluoroborates.
K. R. Buszek, N. Brown, Org. Lett., 2007, 9, 707-710.

Lewis-acid catalysts such as AlMe₃, AlMe₂Cl, and BPh₃ significantly improve the efficiency of the nickel-catalyzed aryl- and alkenylcyanation of alkynes. Electron-rich cyanides, which exhibit poor reactivity in the absence of Lewis acids, readily undergo the arylcyanation reaction under the newly disclosed conditions.
Y. Nakao, A. Yada, S. Ebata, T. Hiyama, J. Am. Chem. Soc., 2007, 129, 2428-2429.

(E)- or (Z)-trisubstituted α,β-unsaturated esters have been prepared in three steps from N-protected glycine. The key step is the highly selective enol tosylation of γ-amino β-keto esters followed by an effective Suzuki-Miyaura coupling reaction with a variety of aryl boronic acids.
J. Baxter, D. Steinhuebel, M. Palucki, I. W. Davies, Org. Lett., 2005, 7, 215-218.

1,1-diarylpropadienes and 1,3-diarylpropynes can be prepared by the sequential lithiation of 1-aryl-1-propynes, transmetalation, and the corresponding Pd(0)-catalyzed cross-coupling with aryl halides.
S. Ma, Q. He, X. Zhang, J. Org. Chem., 2005, 70, 3336-3338.

Stereospecific coupling reactions of readily available alkenylsilanes have been developed.
S. E. Denmark, J. Am. Chem. Soc., 1999, 121, 5821-5822.

A mild, stereospecific cross-coupling of unsymmetrical 1,4-bissilyl-1,3-butadienes has been developed. A selective cross-coupling under mildly basic conditions afforded 4-aryl-1,3-dienylsilanes in excellent yield for a wide range coupling partners. The subsequent cross-coupling of the 4-aryl-1,3-dienylsilanes could be effected cleanly by the action of TBAF with electron-rich or electron-poor halides.
S. E. Denmark, S. A. Tymonko, J. Am. Chem. Soc., 2005, 127, 8004-8005.

The rhodium-catalyzed reaction of aryl boronic acids with internal alkynes and acrylates in water gives the domino coupling products. The reaction demonstrates that water offers the possibility to discover novel transformations.
T. Kurahashi, H. Shinokubo, A. Osuka, Angew. Chem. Int. Ed., 2006, 45, 6336-6338.

Privileged allylic amine structures can be constructed in a regioselective, stereoselective, and diversity-oriented manner by a novel palladium-catalyzed four-component assembly based on allenylboronate platform. A short synthesis of rolipram is also demonstrated.
K. Tonogaki, K. Itami, J.-I. Yoshida, J. Am. Chem. Soc., 2006, 128, 1464-1465.

Homoallylic α-amino esters and amines were prepared via a Pd(II)-catalyzed coupling of 1,2-nonadiene and boronic acids with ethyl iminoacetate or aliphatic, aromatic, and heteroaromatic imines.
C. D. Hopkins, H. C. Malinakova, Org. Lett., 2006, 8, 5971-5974.

Arylboronate esters bearing a pendant Michael-type acceptor olefin undergo a transmetalation with a rhodium-based catalytic complex. These organorhodium intermediates can cyclize onto nonterminal acetylenes in good to excellent yields.
M. Lautens, T. Marquardt, J. Org. Chem., 2004, 69, 4607-4614.

A mild, Pd/C-catalyzed Suzuki-Miyaura coupling of 2-iodocycloenones with arylboronic acids is described. Notably, the procedure features inexpensive reagents, reactions under air, and solvents with low toxicity. In addition, the Pd/C could be reused at least five times.
F.-X. Felpin, J. Org. Chem., 2005, 70, 8575-8578.