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Alkenylation, 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)

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 Zweifel reaction is a powerful transition-metal-free alternative to the Suzuki-Miyaura reaction for the synthesis of alkenes. This transition-metal-free coupling process enables the coupling of Grignard reagents or organolithiums for an enantiospecific synthesis of a wide variety of functionalized acyclic and cyclic olefin products.
R. J. Armstrong, W. Niwetmarin, V. K. Aggarwal, Org. Lett., 2017, 19, 2762-2765.

A Ni-catalyzed Hiyama coupling of aryl halides with cheap, nontoxic, and stable vinyltrimethoxysilane as the vinyl donor proceeds under mild and ligand-free conditions. The method provides a diverse variety of styrene derivatives in high yields with excellent functional group compatibility.
S. Wei, Y. Mao, S.-L. Shi, Synlett, 2021, 32, 1670-1674.

A mild nickel-catalyzed reductive cross-coupling between (hetero)aryl bromides and vinyl acetate provides a variety of vinyl arenes, heteroarenes, and benzoheterocycles. Importantly, dimethyl isosorbide as solvent makes this protocol more sustainable.
M. Su, X. Huang, C. Lei, J. Jin, Org. Lett., 2022, 24, 354-358.

A bench-stable, crystalline vinyl thianthrenium salt can be readily prepared from ethylene gas at atmospheric pressure in one step and is broadly useful in annulation chemistry of (hetero)cycles, N-vinylation of heterocyclic compounds, and palladium-catalyzed cross-coupling reactions.
F. Juliá, J. Yan, F. Paulus, T. Ritter, J. Am. Chem. Soc., 2021, 143, 12992-12998.

Diaryl-, divinyl-, and dialkylindium compounds undergo a palladium-catalyzed cross-coupling reaction with aryl halides in aqueous THF to provide the corresponding coupling product in excellent yield. A wide range of functional groups are tolerated. The indium compounds can be generated from indium trichloride and two equimolar amounts of a Grignard reagent.
K. Takami, H. Yorimitsu, H. Shinokubo, S. Matsubara, K. Oshima, Org. Lett., 2001, 3, 1997-1999.

In Suzuki-Miyaura coupling, Z-alkenyl halides can easily undergo Z-to-E isomerization, the extent of which is dictated mainly by the ligand on palladium. Pd(P(o-Tol)3)2 as catalyst of choice leads to the desired products under mild conditions and in high yields that, in most cases, retain their Z-olefin geometry.
G.-P. Lu, K. R. Voigtritter, C. Cai, B. H. Lipshutz, J. Org. Chem., 2012, 77, 3700-3703.

A stereoconvergent, nickel-catalyzed Suzuki-Miyaura cross-coupling enables the conversion of a wide range of alkenyl ethers and aryl boronic esters for the synthesis of variously substituted styrene derivatives. A mixture of E/Z isomers of alkenyl ethers can be employed, thereby circumventing the stereodefined synthesis of starting materials.
G.-M. Ho, H. Sommer, I. Marek, Org. Lett., 2019, 21, 2913-2917.

Cross-coupling reactions of vinyl ethers with aryl Grignard reagents are efficiently catalyzed by anionic diarylrhodium complexes, generated in situ from [RhCl(cod)]2 and the aryl Grignard reagents. In this catalytic system, vinyl-O bonds were preferably cleaved over Ar-O or Ar-Br bonds.
T. Iwasaki, Y. Miyata, R. Akimoto, Y. Fujii, H. Kuniyasu, N. Kambe, J. Am. Chem. Soc., 2014, 136, 9260-9263.

Highly Stereoselective Hydrocarbation of Terminal Alkynes via Pt-Catalyzed Hydrosilylation/Pd-Catalyzed Cross-Coupling Reactions
S. E. Denmark, Z. Wang, Org. Lett., 2001, 3, 933-935.

The use of the σ-donating DMA solvent is crucial for high selectivity in a simple, mild, and efficient Pd-catalyzed Heck reaction, that delivers (E)-styrenyl products for electronically nonbiased olefin substrates bearing a range of useful functionality in high yields. Further studies suggest that the catalyst distinguishes between β-hydrogens on the basis of their relative hydridic character.
E. W. Werner, M. S. Sigman, J. Am. Chem. Soc., 2011, 133, 9692-9695.

[Rh(cod)OH]2 catalyzes an olefination of aliphatic aldehydes with arylboroxines in air and neutral conditions in the absense of external ligands or additives to provide aryl olefins in an efficient manner with a good functional group tolerance. The mechanism involves a Rh(I)-catalyzed 1,2-addition and a Rh(III)-catalyzed elimination.
Z. Zhang, J. Jia, F. Hu, Y. Xia, Org. Lett., 2023, 25, 3228-3233.

A B(C6F5)3-catalyzed E-selective isomerization of readily accessible allyl silanes and subsequent Hiyama coupling of the versatile alkenyl silane intermediates provide a broad range of styrene derivatives.
B. A. Kustiana, R. L. Melen, L. C. Morrill, Org. Lett., 2022, 24, 8694-8697.

Low-toxicity chromium(II) chloride catalyzes very fast coupling reactions of various (hetero)arylmagnesium reagents with N-heterocyclic halides, aromatic halogenated ketones or imines, and alkenyl iodides at room temperature. Remarkably, much lower amounts of homo-coupling side products are obtained compared to related iron, cobalt, or manganese cross-couplings.
A. K. Steib, O. M. Kuzmina, S. Fernandez, D. Flubacher, P. Knochel, J. Am. Chem. Soc., 2013, 135, 15346-15349.

Aryl Grignard reagents react stereospecifically with alkenyl halides in the presence of manganese chloride as catalyst to afford cross-coupled products in good yields.
G. Cahiez, O. Gager, F. Lecomte, Org. Lett., 2008, 10, 5255-5256.

Sarcosine is an excellent ligand for cobalt-catalyzed carbon-carbon cross-coupling of Grignard reagents with allylic and vinylic bromides. The system performs efficiently when phenyl and benzyl Grignards are coupled with alkenyl bromides. Notably, previously unachievable Co-catalyzed coupling of allylic bromides with Grignards to linearly coupled α-products was also realized.
R. Frlan, M. Sova, S. Gobec, G. Stavber, Z. Časar, J. Org. Chem., 2015, 80, 7803-7809.

Aryl nonaflates are employed as electrophiles in the Pd-catalyzed cross-coupling with tosylhydrazones affording highly substituted olefins. Addition of LiCl and the presence of small amounts of water are required to accomplish the coupling successfully. Under the optimized conditions, the reactions proceed with high yield and also high stereoselectivity depending on the nature of the coupling partners.
J. Barluenga, L. Florentino, F. Aznar, C. Valdes, Org. Lett., 2011, 13, 510-513.

A diastereodivergent hydroarylation of terminal alkynes allows highly selective synthesis of both E and Z diastereoisomers of aryl alkenes, from the same set of starting materials, using the same combination of palladium and copper catalysts. The selectivity is controlled by the stoichiometry of the alcohol additive. The reactions tolerates esters, nitriles, alkyl halides, epoxides, carbamates, acetals, ethers, silyl ethers, and thioethers.
M. K. Armstrong, M. B. Goodstein, G. Lalic, J. Am. Chem. Soc., 2018, 140, 10233-10241.

A diastereodivergent hydroarylation of terminal alkynes allows highly selective synthesis of both E and Z diastereoisomers of aryl alkenes, from the same set of starting materials, using the same combination of palladium and copper catalysts. The selectivity is controlled by the stoichiometry of the alcohol additive. The reactions tolerates esters, nitriles, alkyl halides, epoxides, carbamates, acetals, ethers, silyl ethers, and thioethers.
M. K. Armstrong, M. B. Goodstein, G. Lalic, J. Am. Chem. Soc., 2018, 140, 10233-10241.

A bimetallic catalyst system composed of a group 4 metallocene difluoride and palladium dichloride enables a reductive cross-coupling of alkynes and aryl halides to provide (E)-alkenes in the presence of a hydrosilane and NaF. This reaction proceeds via an in situ generated alkenyl metallocene intermediate derived from the group 4 metallocene difluoride.
K. Takahashi, H. Morishita, Y. Ogiwara, N. Sakai, J. Org. Chem., 2018, 83, 13734-13742.

A highly efficient palladium-catalyzed cross-coupling reaction of alkenyldimethyl(2-pyridyl)silanes with organic halides has been developed. The potentially occurring two reaction pathways (carbometalation and transmetalation) were perfectly controlled by simply changing the additives.
K. Itami, T. Nokami, J.-i. Yoshida, J. Am. Chem. Soc., 2001, 123, 5600-5601.

A synthetically useful nonfluoride-activated, silicon-based, cross-coupling reaction employs inexpensive, commercially available reagents. The successful coupling of in situ generated silyloxides also demonstrates the mechanistically fascinating duality of the silanol moiety as a prosthetic group for controlled carbon-carbon bond formation and as an activator for the coupling.
S. E. Denmark, R. F. Sweis, J. Am. Chem. Soc., 2001, 123, 6439-6440.

The combination of palladium catalysis and iridium photocatalysis enables a general catalytic anti-hydroarylation of electron-deficient internal alkynes with a broad range of arylboronic acids. The reaction of ortho-substituted boronic acids provides pharmaceutically relevant heterocyclic cores via a cascade process.
J. Corpas, P. Mauleón, R. G. Arrayás, J. C. Carretero, Org. Lett., 2020, 22, 6473-6478.

A multicatalytic isomerization/cross-coupling sequence enables a stereoselective coupling of readily available alkenyl methyl ethers with various Grignard reagents to provide highly substituted alkenes. A cationic iridium catalyst for the stereoselective isomerization of allyl methyl ethers to methyl vinyl ethers is compatible with a nickel catalyst for the subsequent cross-coupling.
C. Romano, C. Mazet, J. Am. Chem. Soc., 2018, 140, 4743-4750.

An aqueous rhodium-catalyzed coupling reaction of arylboronic acids and styrenyl olefins provides Heck-type products. When an enolizable functionality is present within the aromatic ring, the addition-hydrolysis pathway occurs to give hydrophenylated compounds. The use of water is crucial since no reaction occurs under analogous conditions in organic solvents.
M. Lautens, A. Roy, K. Fukuoka, K. Fagnou, B. Martín-Matute, J. Am. Chem. Soc., 2001, 123, 5358-5359.

Hydrosilylation of an alkynylboronic ester enables a rapid and stereodefined synthesis of MIDA-boryl vinylsilanes. Subsequent selective cross-couplings in a two-step bidirectional sequence provide a rapid and high-yielding synthesis of complex styrenes.
M. G. McLaughlin, C. A. McAdam, M. J. Cook, Org. Lett., 2015, 17, 10-13.

A direct cobalt-catalyzed vinylation of various aromatic halides using β-halostyrene proceeded smoothly with a total retention of the double bond configuration in the presence of triphenylphosphine as ligand. This procedure offers a new route to the stereoselective synthesis of functionalized stilbenes.
A. Moncomble, P. Le Floch, A. Lledos, C. Gosmini, J. Org. Chem., 2012, 77, 5056-5062.

The presence of FeCl3/CuTC enables an efficient coupling of functionalized aryl Grignard reagents and 1-arylvinyl halides to access 1,1-diarylethylenes of biological interest. This bimetallic system proved to be superior to the use of Fe or Cu catalyst alone. The synthetic utility of this protocol is illustrated in the field of steroid chemistry.
A. Hamze, J.-D. Brion, M. Alami, Org. Lett., 2012, 14, 2782-2785.

A nickel-catalyzed addition of arylboron reagents to ketones provides olefins. The neutral reaction conditions allow acidic protons of alcohols, phenols, and malonates to be present, and fragile structures are also tolerated.
C. Lei, Y. J. Yip, J. S. Zhou, J. Am. Chem. Soc., 2017, 139, 6086-6089.

A palladium-catalyzed ligand-promoted C-C bond cleavage enables a Mizoroki-Heck reaction of unstrained aryl ketones with acrylates/styrenes to afford alkene products in very good yields.
M.-L. Wang, H. Xu, H.-Y. Li, B. Ma, Z.-Y. Wang, X. Wang, H.-X. Dai, Org. Lett., 2021, 23, 2147-2152.

A one-pot regioselective allene hydrosilylation/Pd(0)-catalyzed cross-coupling protocol affords functionalized 1,1-disubstituted alkenes with excellent regiocontrol. The regioselectivity of this hydroarylation is primarily governed by N-heterocyclic carbene (NHC) ligand identity in the hydrosilylation step and is preserved in the subsequent cross-coupling reaction.
Z. D. Miller, J. Montgomery, Org. Lett., 2014, 16, 5486-5489.

A versatile, palladium-catalyzed cross-coupling reaction of hydrazones with aryl halides in the absence of external ligand allows the synthesis of substituted olefins, which are difficult to access from other traditional methods and are not synthesized by employing similar coupling reactions. Application of the present methodology is validated in tandem reaction of ketones to the corresponding substituted olefins in a single pot experiment.
D. P. Ojha, K. R. Prabhu, J. Org. Chem., 2012, 77, 11027-11028.

A PdCl2(MeCN)2/Xphos/NaOtBu/F-benzene system enabled the coupling of sterically hindered N-tosylhydrazones featuring ortho/ortho′-substituents on the aromatic ring with various substituted aryl halides in a sealed tube. This protocol has been applied successfully to the synthesis of a xanthene derivative.
M. Roche, A. Hamze, O. Provot, J.-D. Brion, M. Alami, J. Org. Chem., 2013, 78, 445-454.

A stable palladium nanocatalyst was used for an efficient synthesis of polysubstituted olefins from N-tosylhydrazones and aryl iodides. The nanocatalyst can easily be recovered and reused without any apparent loss in size and catalytic activity.
D. Ganapathy, G. Sekar, Org. Lett., 2014, 16, 3856-3859.

Rhodium-catalyzed regioselective arylzincation of terminal allenes affords synthetically useful functionalized allylzinc reagents, which can be protonated or react with various electrophiles such as carbonyl compounds and acetonitrile.
Y. Yoshida, K. Murakami, H. Yorimitsu, K. Oshima, J. Am. Chem. Soc., 2010, 132, 8878-8879.

An aerobic boron Heck reaction with cyclobutene forms exclusively linear 1-aryl-1,3-dienes using (hetero)arylboronic acids, or 1,3,5-trienes using alkenylboronic acids, rather than typical Heck products (i.e., substituted cyclobutenes).
N. J. McAlpine, L. Wang, B. P. Carrow, J. Am. Chem. Soc., 2018, 140, 13634-13639.

A wide range of aryl and vinylic halides react with 1,1-dimethylallene and potassium carbonate in the presence of Pd(dba)2 in N,N-dimethylacetamide to provide dienes in very good yields. Tetramethylallene, 1-methyl-1-phenylallene, 1-methyl-3-phenylallene, and 1-cyclohexylallene also react with aryl and vinylic halides to give diene products.
H.-M. Chang, C.-H. Cheng, J. Org. Chem., 2000, 65, 1767-1773.

A base-free rhodium-catalyzed Mizoroki-Heck reaction of potassium aryltrifluoroborates with alkenes in the presence of acetone as green "oxidant" constitutes an interesting alternative to conventional olefinations using aryl halides thanks to the ready availability of organoboranes.
R. Martinez, F. Voica, J.-P. Genet, S. Darses, Org. Lett., 2007, 9, 3213-3216.

A highly selective Rh(I)-catalyzed defluorinative coupling of boronic acids with (E)-β-monofluoroacrylates provides trisubstituted (Z)-alkene products in excellent dr with an inversion of double bond geometry. Experimental and computational studies established that Rh(I)-facilitated β-F elimination is favored over competing β-H elimination and protodemetalation.
Y. Zong, Y. Tang, G. C. Tsui, Org. Lett., 2022, 24, 6380-6385.

A gold-catalyzed intermolecular hydroarylation of propiolic acid with arylboronic acids is highly regioselective and occurs at the less electrophilic carbon to afford α-aryl acrylic acids in attractive yields. This carboxylic acid-directed arylation offers easy access to NSAID precursors.
K. S. Basha, R. Balamurugan, Org. Lett., 2023, 25, 4803-4807.

An I(III)-mediated skeletal reorganization of silyl enol ethers enables a formal enone α-arylation. This metal-free transformation offeres mild conditions, good yields, and high stereoselectivities for β-substituted enones.
B. S. Martins, D. Kaiser, A. Bauer, I. Tiefenbrunner, N. Maulide, Org. Lett., 2021, 23, 2094-2098.

Pd(OAc)2 in the presence of a BIAN ligand is an efficient catalyst system for the base-free oxidative Heck reaction that outperforms the currently available catalysts for the more challenging substrates studied. The catalyst system is highly selective, and works at room temperature with dioxygen as the oxidant.
A. L. Gottumukkala, J. F. Teichert, D. Heijnen, N. Eisink, S. van Dijk, C. Ferrer, A. van den Hoogenband, A. J. Minnaard, J. Org. Chem., 2011, 76, 2937-2941.

α-Haloalkenyl acetals react smoothly with (het)aryl boronic acids, aryl boronates, or B-alkyl-9-borabicyclo[3.3.1]nonanes through Pd-catalyzed Suzuki cross-coupling in very good yields. This mild protocol features a broad substrate scope and good functional-group compatibility, and is easily scaled up.
L. Zhang, Synlett, 2021, 32, 723-727.

In the TMSOTf-mediated catalytic carbocupration of ynoates, catalyst loadings as low as 5 mol % readily allow for high yields and diastereoselectivities for a series of aromatic Grignard reagents. A vicinally functionalization is possible via initial TMSOTf-mediated catalytic carbocupration followed by a secondary electrophilic capture of the TMS allenoate intermediate.
A. J. Mueller, M. P. Jennings, Org. Lett., 2007, 9, 5327-5329.

An (E)- and (Z)-stereocomplementary preparative method for α,β-disubstituted α,β-unsaturated esters is performed via three general and robust reaction sequences: Ti-Claisen condensation (formylation) of esters to give α-formyl esters, (E)- and (Z)-stereocomplementary enol tosylation using TsCl-N-methylimidazole-Et3N and LiOH, and stereoretentive Suzuki-Miyaura cross-coupling.
H. Nakatsuji, H. Nishikado, K. Ueno, Y. Tanabe, Org. Lett., 2009, 11, 4258-4261.

A mild and efficient protocol for palladium-catalyzed oxidative Heck reactions of arylboronic acids with both electron-rich and -deficient olefins works in the absence of a base, oxygen, or other external oxidants. With a wide variety of substrates tolerated, the method broadens the scope of palladium-catalyzed coupling reactions.
J. Ruan, X. Li, O. Saidi, J. Xiao, J. Am. Chem. Soc., 2008, 130, 2424-2425.

The combination of [Ru(p-cymene)Cl2]2/triethylphosphine/lithium carbonate catalyzes a coupling of aryl bromides with unprotected 2-arylacrylic acids to form (Z)-diarylacrylic acids in high yields. The reaction tolerates a wide range of functional groups. The vinylic C-H activation proceeds via base-assisted cyclometalation rather than a Heck-type mechanism, which explains its stereoselectivity.
F. Belitz, A.-K. Seitz, J. F. Goebel, Z. Hu, L. K. Goossen, Org. Lett., 2022, 24, 3467-3470.

A Pd-catalyzed oxidative cross-coupling reaction of arylboronic acids with α-diazoesters using molecular oxygen as the reoxidant gives E-α,β-diarylacrylates in good yields and very high E-to-Z selectivity.
Y.-T. Tsoi, Z. Zhou, A. S. C. Chan, W.-Y. Yu, Org. Lett., 2010, 12, 4506-4509.

A carboxylic-acid-directed oxidative Heck reaction enables a direct synthesis of 4-aryl-3-butenoic acids in good yields.
S. Yang, L. Liu, Z. Zhou, Z. Huang, Y. Zhao, Org. Lett., 2021, 23, 296-299.

A copper(II)-catalyzed intermolecular three-component oxyarylation of allenes using arylboronic acids as a carbon source and TEMPO as an oxygen source proceeded under mild conditions with high regio- and stereoselectivity and functional group tolerance.
T. Itoh, Y. Shimizu, M. Kanai, Org. Lett., 2014, 16, 2736-2739.

Arylations of electron-rich heteroatom-substituted olefins were performed with electron-rich arylboronic acids via palladium(II) catalysis. This mild protocol, which offers access to functionalized enamides, exploits oxygen gas for reoxidation and a stable 1,10-phenanthroline bidentate ligand to promote the palladium(II) regeneration and to control the regioselectivity.
M. M. S. Andappan, P. Nilsson, H. v. Schenck, M. Larhed, J. Org. Chem., 2004, 69, 5212-5218.

In a highly regio- and stereoselective hydroarylation, hydroalkenylation, and hydrobenzylation of ynol ethers, a Pd-catalyzed reductive addition of organohalides, including aryl, alkenyl, and benzyl halides, in the presence of 2-propanol gives α,β- and β,β-disubstituted olefinic ethers in good yields.
W. Cui, J. Yin, R. Zheng, C. Cheng, Y. Bai, G. Zhu, J. Org. Chem., 2014, 79, 3487-3493.

A highly regio- and stereoselective coupling of (Z)-1,2-bis(aryl(alkyl)thio)alkenes and Grignard reagents in the presence of a Ni catalyst under mild conditions enables an efficient route for the synthesis of (Z)-vinylic sulfides. (Z)-vinylic sulfides are important intermediates in the synthesis of tri- and tetrasubstituted alkenes.
J. Chen, S. Chen, X. Xu, Z. Tang, C.-T. Au, R. Qiu, J. Org. Chem., 2016, 81, 3246-3255.

An efficient Pd-catalyzed addition of boronic acids to silylacetylenes provides β,β-disubstituted (E)- or (Z)-alkenylsilanes in good yields with excellent regio- and stereoselectivity under mild reaction conditions. Moreover, a sequential Pd-catalyzed boron addition/N-halosuccinimide-mediated halodesilylation reaction results in a stereodivergent approach to β,β-disubstituted alkenyl halides as versatile synthetic intermediates.
W. Kong, C. Che, J. Wu, L. Ma, G. Zhu, J. Org. Chem., 2014, 79, 5799-5805.

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 Pd(0)-catalyzed Suzuki-Miyaura coupling reaction of aryl boronic acids with vinyl tosylate provides access to styrene derivatives in good yields. The easily accessible vinyl tosylate represents a stable and less toxic alternative to the vinyl halides and the triflate/nonaflate derivatives. Furthermore, this methodology was expanded using the similar and also readily available 2,2-difluorovinyl tosylate.
T. M. Gøgsig, L. S. Søbjerg, A. T. Lindhardt (neé Hansen), K. L. Jensen, T. Skrydstrup, J. Org. Chem., 2008, 73, 3404-3410.

A variety of aromatic iodides and bromides undergo cross-coupling with divinyltetramethyldisiloxane (DVDS) to give styrenes in good yields in the presence of potassium trimethylsilanoate and catalytic amounts of Pd(dba)2. Triphenylphosphine oxide is needed to extend catalyst lifetime.
S. E. Denmark, C. R. Butler, J. Am. Chem. Soc., 2008, 130, 3690-3704.

Fluoride-free cross-coupling reactions of alkenyltrialkoxysilanes with aryl iodides, bromides, and chlorides are performed under ligand-free conditions with low Pd loadings on water using sodium hydroxide as activator and tetra-n-butylammonium bromide as additive at 120°C under conventional or microwave heating.
E. Alacid, C. Nájera, J. Org. Chem., 2008, 73, 2315-2322.

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.

A sequential hydroboration/Suzuki-Miyaura coupling of ynol ethers allows a highly regio- and stereoselective synthesis of stereodefined β,β-disubstituted alkenyl ethers. A number of functional groups are well-tolerated under the reaction conditions. Furthermore, the reaction enables a facile entry to labile diarylacetaldehydes by TFA-mediated hydrolysis of the β,β-disubstituted vinyl ethers.
W. Cui, M. Mao, Z. He, G. Zhu, J. Org. Chem., 2013, 78, 9815-9821.

The reaction of acetanilides with symmetrical as well as unsymmetrical alkynes in the presence of [{RuCl2(p-cymene)}2], pivalic acid, and AgSbF6 in i-PrOH provides ortho-alkenylated acetanilides in a highly regio- and stereoselective manner. The products can be converted into ortho-alkenylated anilines in the presence of HCl.
R. Manikandan, M. Jeganmohan, Org. Lett., 2014, 16, 912-915.

A ruthenium-catalyzed chelation-assisted C-H bond activation of aromatic ketones followed by reaction with olefins provides Heck-type products in good to excellent yields with a high regio- and stereoselective manner.
K. Padala, M. Jeganmohan, Org. Lett., 2011, 13, 6144-6147.

Rh(III)-catalyzed olefination of N-sulfonyl imines using acrylates and styrenes enables the synthesis of ortho-functionalized benzaldehydes via a chelation assisted C-H olefination/in situ hydrolysis process.
T. Zhang, L. Wu, X. Li, Org. Lett., 2013, 15, 6294-6297.

Ruthenium-catalyzed oxidative C-H bond formation of N-methoxybenzamides using an oxidizing directing group gives ortho-substituted Heck-type products with acrylates in MeOH, whereas reactions with styrene (or norbornadiene) in CF3CH2OH affords 3,4-dihydroisoquinolinones.
B. Li, J. Ma, N. Wang, H. Feng, S. Xu, B. Wang, Org. Lett., 2012, 14, 736-739.

A novel chelate-controlled intermolecular oxidative Heck reaction proceeds with a wide range of nonresonance stabilized α-olefin substrates and organoboron reagents to afford internal olefin products in good yields and outstanding regio- and E:Z stereoselectivities. Pd-H isomerization, common in many Heck reactions, is not observed under these mild, oxidative conditions.
J. H. Delcamp, A. P. Brucks, M. C. White, J. Am. Chem. Soc., 2008, 130, 11270-11271.

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.

With certain substituent patterns, benzyl benzyl sulfone systems give unexpectedly high Z-stereoselectivity in the Meyers variant of the Ramberg-Bäcklund reaction. A range of sulfones were explored to rationalize this unprecedented selectivity for Z-stilbene systems.
J. S. Foot, G. M. P. Giblin, A. C. Whitwood, R. J. K. Taylor, Org. Biomol. Chem., 2005, 3, 756-763.

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.

A Pd(0)-catalyzed cross-coupling reaction of diazirines with aryl halides under microwave irradiation affords substituted olefins in good yields via a migratory insertion of a Pd carbene intermediate.
H. Jiang, H. Huang, H. Cao, C. Qi, Org. Lett., 2010, 12, 5561-5563.

PdCl2(MeCN)2 in combination with dppp is an efficient catalyst for the coupling of sterically hindered N-arylsulfonylhydrazones with aryl halides providing a flexible and convergent access to tetrasubstituted olefins related to iso-combretastatin A4 in good yields.
E. Brachet, A. Hamze, J.-F. Peyrat, J.-D. Brion, M. Alami, Org. Lett., 2010, 12, 4042-4045.

TsCl coupled with NMI forms a highly reactive N-sulfonylammonium intermediate. β-Ketoesters undergo (E)-selective tosylation using TsCl-NMI-Et3N and (Z)-selective tosylation using TsCl-NMI-LiOH in good yield. Stereoretentive Negishi and Sonogashira couplings using enol tosylates proceed successfully to give trisubstituted α,β-unsaturated esters.
H. Nakatsuji, K. Ueno, T. Misaki, Y. Tanabe, Org. Lett., 2008, 10, 2131-2134.

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.

A stereoselective arylation and vinylation of alkenes without transition-metal catalysts takes place through an interesting NBS-promoted semipinacol rearrangement under mild conditions and a subsequent unusual NaOH-mediated Grob fragmentation.
D.-Y. Yuan, Y.-Q. Tu, C.-A. Fan, J. Org. Chem., 2008, 73, 7797-7799.

The PdCl2/PtBu3 catalytic system with copper(I) iodide and cesium fluoride in DMF is most effective for coupling aryl bromides, while Pd(PPh3)4 is optimal when coupling iodides and triflates. The combination of copper(I) iodide and cesium fluoride should allow the synthesis of sterically hindered systems and promotes electronically disfavored coupling reactions.
S. P. H. Mee, V. Lee, J. E. Baldwin, Angew. Chem. Int. Ed., 2004, 43, 1132-1136.

A Pd(PPh3)4-catalyzed reaction between α-diazocarbonyl compounds and arylboronic acids leads to cross-coupled products in good yields.
C. Peng, Y. Wang, J. Wang, J. Am. Chem. Soc., 2008, 130, 1566-1567.

A regio- and stereoselective rhodium-catalyzed reaction of propargylic alcohols with boronic acids enables the synthesis of trisubstituted allylic alcohols. The utility of these synthons is demonstrated in a convenient synthesis of indenes and quinolines.
J. Panteleev, R. Y. Huang, E. K. J. Lui, M. Lautens, Org. Lett., 2011, 13, 5314-5317.

A copper-catalyzed highly anti-selective radical 1,2-alkylarylation of terminal alkynes with aryl boronic acids and alkyl bromides providesg facile access to various stereodefined trisubstituted alkenes in high yield under mild reaction conditions. The reaction exhibits high compatibility with a wide range of terminal alkynes and diverse aryl boronic acids.
J.-B. Tang, J.-Q. Bian, Y.-S. Zhang, Y.-F. Cheng, H.-T. Wen, Z.-L. Yu, Z.-L. Yu, Z.-L. Li, Q.-S. Gu, G.-Q. Chen, X.-Y. Liu, Org. Lett., 2022, 24, 2536-2540.

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.

Synthesis of Styrenes Using Ruthenium-Catalyzed Ring-Closing Enyne Metathesis
K. Yoshida, Y. Shishikura, H. Takahashi, T. Imamoto, Org. Lett., 2008, 10, 2777-2780.

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.

The reaction of organocerium reagents, generated in situ from aryl and heteroaryl lithium compounds, with cycloalkanones proceeds cleanly to provide alkoxides. Addition of MsCl or SOCl2 with DBU gave aryl-substituted cycloalkenes in good yields. A short total synthesis of (±)-laurokamurene B is described.
J. Tallineau, G. Bashiardes, J.-M. Coustard, F. Lecornué, Synlett, 2009, 2761-2764.

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.

A Pd-catalyzed hydrogenation of potassium (3,3,3-trifluoroprop-1-yn-1-yl)trifluoroborate provides either the (Z)- or (E)-isomer of the vinylborate in >98% purity. Coupling with bromo- and iodoarenes provides a variety of (Z)- or (E)-β-trifluoromethylstyrenes. Also, a safe synthesis of the alkynyltrifluoroborate has been described.
P. V. Ramachandran, W. Mitsuhashi, Org. Lett., 2015, 17, 1252-1255.

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.

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.

Monofluorovinyl tosylate is a practical vinyl fluoride building block to couple with various arylboronic acids in the presence of a palladium catalyst. A high stereoselectivity in the synthesis of 2-aryl-1-fluoroethene derivatives was achieved. This approach is also applicable to the synthesis of 2,2-diaryl-1-fluoroethenes in good yields.
H. Zhang, C.-B. Zhou, Q.-Y. Chen, J.-C. Xiao, R. Hong, Org. Lett., 2011, 13, 560-563.

A gem-difluoroolefination of trifluoroacetaldehyde N-triftosylhydrazone with organoboronic acids - including alkylboronic acids - is operationally simple, free of transition metals, and suitable for a broad range of substrates. Moreover, the utility of the products was demonstrated by further conversion of the gem-difluorovinyl group.
Y. Ma, B. R. P. Reddy, X. Bi, Org. Lett., 2019, 21, 9860-9863.

A highly diastereoselective rhodium(I)-catalyzed C-F bond functionalization of gem-difluoroalkenes with arylboronic acids provides valuable monofluoroalkenes. A Rh(I)/BINAP catalytic system enables the C-F bond arylation of both trisubstituted β,β-difluorostyrenes and tetrasubstituted β,β-difluoroacrylates in >99:1 dr via a migratory insertion/β-F elimination mechanism.
H. Tan, Y. Zong, Y. Tang, G. C. Tsui, Org. Lett., 2023, 25, 877-882.

An efficient Pd-catalyzed stereoselective vinyltrifluoromethylation of aryl halides, through decarboxylative cross-coupling with 2-(trifluoromethyl)acrylic acid offers ready availability of the starting materials, high level of functional group tolerance, and excellent E/Z selectivity. This protocol is a safe and operationally convenient strategy for an efficient synthesis of vinyltrifluoromethyl derivatives.
S. Kathiravan, I. A. Nicholls, Org. Lett., 2015, 17, 1874-1877.

An operationally simple Pd-catalyzed three component reaction involving terminal alkynes, boronic acids, and perfluoroalkyl iodides gives trisubstituted perfluoroalkenes in a highly regio- and stereocontrolled manner by simultaneous additions across the triple bond in a radical-mediated process. The reaction is broad in scope and tolerates many functional groups.
Z. Li, A. García-Domínguez, C. Nevado, J. Am. Chem. Soc., 2015, 137, 11610-11613.

A cobalt-catalyzed ynamide carbozincation provides diverse 3-aryl enamides with mild reaction conditions and good functional-group tolerance. This reaction displays an excellent regio- and total stereoselectivity. Moreover, this approach allows the selective synthesis of biologically relevant 3,5-disubstituted oxazolone frameworks.
R. Sallio, M. Corpet, L. Habert, M. Durandetti, C. Gosmini, I. Gillaizeau, J. Org. Chem., 2017, 82, 1254-1259.

The use of a palladium(II) acetate-organophosphine catalyst system enables an efficient coupling of (1-bromovinyl)phosphonates with aryl boronic acids. A wide range of (1-arylvinyl)phosphonates were prepared in very good yields. The protocol can be effectively scaled up and even allows the use of a (1-chloro­vinyl)phosphonate as the electrophilic coupling partner.
Y. Fang, L. Zhang, X. Jin, J. Li, M. Yuan, R. Li, H. Gao, J. Fang, Y. Liu, Synlett, 2015, 26, 980-984.

α-Phosphonovinyl tosylates can be coupled efficiently with a range of arylboronic acids to provide α-arylethenylphosphonates. The unprecedented procedure exhibits excellent functional group tolerance, giving the terminal vinylphosphonates in good to excellent isolated yields under mild reaction conditions.
Y. Fang, L. Zhang, J. Li, X. Jin, M. Yuan, R. Li, R. Wu, J. Fang, Org. Lett., 2015, 17, 798-801.

[Cp*RhCl2]2 is a very effective catalyst for C-C coupling of quinones with aryl and alkyl boronic acids under mild conditions. This reaction provides a practical, efficient method for the synthesis of aryl- and alkylquinones in good yields at room temperature and under base-free conditions.
D. Wang, B. Ge, L. Du, H. Miao, Y. Ding, Synlett, 2014, 25, 2895-2898.

A scalable, direct functionalization of various quinones with several boronic acids proceeds readily at room temperature in an open flask using catalytic silver(I) nitrate in the presence of a persulfate co-oxidant. The scope with respect to quinones is broad, with a variety of alkyl- and arylboronic acids undergoing efficient cross-coupling.
Y. Fujiwara, V. Domingo, I. B. Seiple, R. Gianatassio, M. Del Bel, P. P. S. Baran, J. Am. Chem. Soc., 2011, 133, 3292-3295.