Suzuki-Miyaura Cross-Coupling Reaction

Suzuki-Miyaura reaction is a palladium catalyzed cross-coupling reaction between organic boron compounds and organic halides.1) The reaction requires an additional base for the activation of the boron compound and proceeds under mild conditions. This relatively simple and versatile C-C bond formation reaction can be extended to various substrates and therefore finds wide application for the synthesis of pharmaceuticals and total synthesis of complex natural products.

The usefulness of this reaction has been well documented by the synthesis of biaryl compounds in 1981,3) triggered by the initial synthesis of dienes using the vinyl-type boron compounds initiated in 1979.2) Eventually the reaction also proved applicable to the coupling reaction of alkyl halides and alkylboranes. Organotrifluoroborates also represent an effective alternative to boronic acids and boronate esters being stable towards numerous reagents and allow the manipulation of functional groups within them.4)
N-Heterocyclic carbenes prepared from imidazolium and imidazolinium salts can also be efficiently employed as ligands in addition to organophosphine compounds.5) Recently, the synthesis of biaryl compounds without the aid of ligands has also been accomplished.6)
It has been recently reported that nickel can also catalyze the above reaction with the same efficiency as the expensive palladium catalysts specially in case of difficult substrates like aryl chlorides in which reaction does not proceed easily with conventional palladium as the catalyst. In addition to being inexpensive, nickel catalysts can also be removed much easily from the reaction system.7)
Proper choice of metals, ligands, bases and solvents enable the widespread application of the Suzuki-Miyaura cross-coupling reaction to various substrates and different synthetic sequences. We provide a wide range of organic boron compounds as coupling partners. In this section, we introduce different varieties of reaction partners in addition to the organoboron compounds, such as metal catalysts and phosphine ligands to explore the versatile applicability of the Suzuki-Miyaura cross-coupling reaction.

Palladium Catalyst

Nickel Catalyst

Phosphine Ligands

N-Heterocyclic Carbene Ligands

Others

Bases & Additives

Palladium Catalyst

A1479 A1479 B2029 B2029 B1676 B1676
B1668 B1668 B3224 B3224 B1374 B1374
B3160 B3160 B2031 B2031 B2016 B2016
B2064 B2064 B2192 B2192 B2161 B2161
B2018 B2018 B3161 B3161 B2055 B2055
B2042 B2042 B1667 B1667 B2026 B2026
C2387 C2387 C2372 C2372 C2406 C2406
C2407 C2407 D2604 D2604 P1490 P1490
P1491 P1491 P1785 P1785 A1424 A1424
P1489 P1489 P1528 P1528 P1870 P1870
P1425 P1425 S0540 S0540 T1350 T1350
T2184 T2184
A1479 Allylpalladium(II) Chloride Dimer
B2029 Benzylbis(triphenylphosphine)palladium(II) Chloride
B1676 Bis(acetonitrile)palladium(II) Dichloride
B1668 Bis(benzonitrile)palladium(II) Dichloride
B3224 Bis[1,2-bis(diphenylphosphino)ethane]palladium(0)
B1374 Bis(dibenzylideneacetone)palladium(0)
B3160 [1,1'-Bis(di-tert-butylphosphino)ferrocene]palladium(II) Dichloride
B2031 [1,4-Bis(diphenylphosphino)butane]palladium(II) Dichloride
B2016 [1,2-Bis(diphenylphosphino)ethane]palladium(II) Dichloride
B2064 [1,1'-Bis(diphenylphosphino)ferrocene]palladium(II) Dichloride Dichloromethane Adduct
B2192 [1,3-Bis(diphenylphosphino)propane]palladium(II) Dichloride
B2161 Bis(methyldiphenylphosphine)palladium(II) Dichloride
B2018 Bis(2,4-pentanedionato)palladium(II)
B3161 Bis(tri-tert-butylphosphine)palladium(0)
B2055 Bis(tricyclohexylphosphine)palladium(II) Dichloride
B2042 Bis(triphenylphosphine)palladium(II) Diacetate
B1667 Bis(triphenylphosphine)palladium(II) Dichloride
B2026 Bis(tri-o-tolylphosphine)palladium(II) Dichloride
C2387 Chloro[[1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](acetanilide)palladium(II)] (This product is unavailable for selling domestically in U.S.)
C2372 Chloro[[1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](N,N-dimethylbenzylamine)palladium(II)] (This product is unavailable for selling domestically in U.S.)
C2406 Chloro[[1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](N,N-dimethyl-3,5-dimethoxybenzylamine)palladium(II)] (This product is unavailable for selling domestically in U.S.)
C2407 Chloro[[1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](4'-methoxyacetanilide)palladium(II)] (This product is unavailable for selling domestically in U.S.)
D2604 Dichloro(1,5-cyclooctadiene)palladium(II)
P1490 Palladium 5% on Carbon (wetted with ca. 55% Water)
P1491 Palladium 10% on Carbon (wetted with ca. 55% Water)
P1785 Palladium 10% on Carbon (wetted with ca. 55% Water) [Useful catalyst for coupling reaction, etc.]
A1424 Palladium(II) Acetate
P1430 Palladium Catalyst Set Palladium(II) Acetate / Allylpalladium(II) Chloride Dimer / Bis(benzonitrile)palladium(II) Dichloride / Bis(dibenzylideneacetone)palladium(0) / [1,1'-Bis(diphenylphosphino)ferrocene]palladium(II) Dichloride Dichloromethane Adduct / Bis(triphenylphosphine)palladium(II) Dichloride / Tetrakis(triphenylphosphine)palladium(0) (includes useful 7 Palladium catalysts)
P1489 Palladium(II) Chloride
P1528 Palladium Hydroxide 20% on Carbon (wetted with ca. 50% Water)
P1870 Palladium(II) Trifluoroacetate
P1425 Poly[N-isopropylacrylamide-co-4-(diphenylphosphino)styrene] Palladium(II) Dichloride (ratio, acrylamide:phosphine=20:2)
S0540 Sodium Tetrachloropalladate(II)
T1350 Tetrakis(triphenylphosphine)palladium(0)
T2184 Tris(dibenzylideneacetone)dipalladium(0)
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Nickel Catalyst

B2225 B2225 B2226 B2226 B1313 B1313
N0096 N0096 B3534 B3534 B1571 B1571
B2225 [1,2-Bis(diphenylphosphino)ethane]nickel(II) Dichloride
B2226 [1,1'-Bis(diphenylphosphino)ferrocene]nickel(II) Dichloride
B1313 [1,3-Bis(diphenylphosphino)propane]nickel(II) Dichloride
N0096 Bis(2,4-pentanedionato)nickel(II) Hydrate
B3534 Bis(tricyclohexylphosphine)nickel(II) Dichloride
B1571 Bis(triphenylphosphine)nickel(II) Dichloride
S0487 Skeletal Nickel Catalyst slurry in Water [Active catalyst for Hydrogenation]
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Phosphine Ligands

B2711 B2711 B2710 B2710 B1405 B1405
B1406 B1406 B1246 B1246 B2709 B2709
B1137 B1137 B2027 B2027 B1959 B1959
B1112 B1112 B1113 B1113 B1982 B1982
B1960 B1960 B2867 B2867 B1138 B1138
D3940 D3940 D3387 D3387 D2411 D2411
D3388 D3388 D3389 D3389 D2535 D2535
D2536 D2536 D2766 D2766 E0519 E0519
T2584 T2584 T1165 T1165 T1643 T1643
T1025 T1025 T1024 T1024 T0519 T0519
T0862 T0862 T1614 T1614 T0861 T0861
B2711 1,1'-Bis(di-tert-butylphosphino)ferrocene
B2710 1,1'-Bis(diisopropylphosphino)ferrocene
B1405 (S)-(-)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl
B1406 (R)-(+)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl
B1246 1,4-Bis(diphenylphosphino)butane
B2709 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene
B1137 1,2-Bis(diphenylphosphino)ethane
B2027 1,1'-Bis(diphenylphosphino)ferrocene
B1959 1,6-Bis(diphenylphosphino)hexane
B1112 (2S,3S)-(+)-1,4-Bis(diphenylphosphino)-2,3-O-isopropylidene-2,3-butanediol
B1113 (2R,3R)-(-)-1,4-Bis(diphenylphosphino)-2,3-O-isopropylidene-2,3-butanediol
B1982 Bis(diphenylphosphino)methane
B1960 1,5-Bis(diphenylphosphino)pentane
B2867 Bis[2-(diphenylphosphino)phenyl] Ether
B1138 1,3-Bis(diphenylphosphino)propane
D3940 Di-tert-butylphenylphosphine
D3387 2-(Di-tert-butylphosphino)biphenyl
D2411 Dicyclohexylphenylphosphine
D3388 2-(Dicyclohexylphosphino)biphenyl
D3389 2-(Dicyclohexylphosphino)-2'-(dimethylamino)biphenyl
D2535 (R)-N,N-Dimethyl-1-[(S)-2-(diphenylphosphino)ferrocenyl]ethylamine
D2536 (S)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine
D2766 4-Diphenylphosphinomethyl Polystyrene Resin cross-linked with 2% DVB (200-400mesh) (0.5-1.0mmol/g)
E0519 Ethyldiphenylphosphine
T2584 Tri-tert-butylphosphonium Tetrafluoroborate
T1165 Tricyclohexylphosphine (contains Tricyclohexylphosphine Oxide) (ca. 18% in Toluene, ca. 0.60mol/L)
T1643 Tri(2-furyl)phosphine
T1025 Tri(m-tolyl)phosphine
T1024 Tri(o-tolyl)phosphine
T0519 Triphenylphosphine
T0862 Tri(p-tolyl)phosphine
T1614 Tris(2,6-dimethoxyphenyl)phosphine
T0861 Tris(4-methoxyphenyl)phosphine
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N-Heterocyclic Carbene Ligands

B3506 B3506 B3157 B3157 D3611 D3611
B3465 B3465 B3158 B3158 D3711 D3711
D3472 D3472 D3446 D3446 D3870 D3870
B3506 1,3-Bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene
B3157 1,3-Bis(2,6-diisopropylphenyl)imidazolinium Chloride
D3611 1,3-Bis(2,6-diisopropylphenyl)imidazolium Chloride
B3465 1,3-Bis(2,6-diisopropylphenyl)imidazol-2-ylidene
B3158 1,3-Bis(2,4,6-trimethylphenyl)imidazolinium Chloride
D3711 1,3-Di-tert-butylimidazolium Tetrafluoroborate
D3472 1,3-Di-tert-butylimidazol-2-ylidene
D3446 1,3-Dimesitylimidazolium Chloride
D3870 1,3-Dimesitylimidazol-2-ylidene
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Others

H1176 H1176 T1848 T1848 T0508 T0508
H1176 Heptadecafluoro-1-octanesulfonyl Fluoride (mixture of n- and iso- isomers)
T1848 Triphenylantimony Diacetate
T0508 Triphenylarsine
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Bases & Additives

B2695 B2695 D0905 D0905 B0468 B0468
B1018 B1018 B0709 B0709 C2430 C2430
C2204 C2204 D1599 D1599 L0222 L0222
M0508 M0508 P0221 P0221 P0081 P0081
S0485 S0485 T0054 T0054 T0057 T0057
B2695 Bathophenanthroline (purified by sublimation)
D0905 Bathophenanthroline
B0468 2,2'-Bipyridyl
B1018 1,8-Bis(dimethylamino)naphthalene [for Dehydrohalogenation]
B0709 tert-Butylamine
C2430 Cesium Acetate
C2204 Cesium Fluoride
D1599 N,N-Diisopropylethylamine
L0222 Lithium Chloride (2.3% in Tetrahydrofuran, ca. 0.5mol/L)
M0508 1-Methylimidazole
P0221 1,10-Phenanthroline Monohydrate
P0081 1,10-Phenanthroline Hydrochloride Monohydrate
S0485 Sodium Methoxide
T0054 Tetrabutylammonium Bromide
T0057 Tetrabutylammonium Iodide
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Classes of Boron Compounds

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Literature

1) Review: A. Suzuki, Chem. Commun., 2005, 4759 [DOI]; A. Suzuki, Yuki Gosei Kagaku Kyokaishi (J. Synth. Org. Chem. Jpn.), 2005, 63, 312; A. Suzuki, Proc. Jpn. Acad., Ser. B, 2004, 80, 359 [DOI]; N. Miyaura, A. Suzuki, Chem. Rev., 1995, 95, 2457 [DOI].
2) N. Miyaura, K. Yamada, A. Suzuki, Tetrahedron Lett., 1979, 20, 3437 [DOI].
3) T. Yanagi, N. Miyaura, A. Suzuki, Synth. Commun., 1981, 11, 513 [DOI].
4) Review: G. A. Molander, N. Ellis, Acc. Chem. Res., 2007, 40, 275 [DOI].
5) Review: E. A. B. Kantchev, C. J. O'Brien, M. G. Organ, Angew. Chem. Int. Ed., 2007, 46, 2768 [DOI].
6) T. Maegawa, Y. Kitamura, S. Sako, T. Udzu, A. Sakurai, A. Tanaka, Y. Kobayashi, K. Endo, U. Bora, T. Kurita, A. Kozaki, Y. Monguchi, H. Sajiki, Chem. Eur. J., 2007, 13, 5937 [DOI].
7) Review: T. Kamikawa, Fain Kemikaru, 2006, 35, 53.

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