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Ferrocene Polyphosphine Ligand Kit
For Palladium-Catalysed C–N And C–C Cross-Couplings.

Air and moisture insensitive auxiliary ligands for highly efficient palladium catalysts. These ultra-low loading (high TONs or TOFs) catalysts have shown excellent activity in Suzuki cross-coupling with aryl bromides and chlorides, Heck vinylation, Heck-Sonogashira alkynylation and allylic amination of allyl acetates (Tsuji–Trost type reactions). Low loadings of the catalysts ensure minimal contamination of the final compounds with palladium and simplify the purification procedures. High stability of the allows to store them for unlimited time without special precautions.
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Tetraphos Fc(P)4

Triphos Fc(P)3

Triphos Fc(P)2PiPr
EN400-15231 EN400-15232 EN400-15233

Tetraphos Fc(P)2(P’)2

Diphos Fc(P)2

Diphos Fc(PFuMe)2
EN400-15234 EN400-15235 EN400-15236
Ligands are available in milligram and multigram quantities.
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EXAMPLES & NOTES:
(J.-C. Hierso et al. Organometallics (2003), 22(22), 4490-4499.)

  • Suzuki cross-coupling with aryl bromides at ultra-low catalyst loadings (L = Tetraphos Fc(P)4 EN400-15231)

R1 R2 Ratio S/Cat. Yield, %
C(=O)Me H 100000 100 (94)a
CN H 100000 100 (87)a
CF3 H 100000 100
OMe H 100000 77
OMe H 10000 100 (92)a

a - isolated yield, conditions: 1 Pd / 1 Tetraphos Fc(P)4: 10-2 - 10-4 mol%;
DMF or xylene, K2CO3, 130 °C, 20h.


  • Suzuki cross-coupling with aryl chlorides (L = Tetraphos Fc(P)4 EN400-15231)

R1 R2 Ratio S/Cat. Yield, %
C(=O)Me OMe 1000 98 (88)a
C(=O)Me OMe 10000 74
CN OMe 1000 89 (83)a

a - isolated yield, conditions: 1 Pd / 1 Tetraphos Fc(P)4 : 10-1 - 10-2 mol%;
DMF or xylene, K2CO3, 130 °C, 20h.


  • Heck reaction at ultralow catalyst loadings (L = Tetraphos Fc(P)4 EN400-15231)

Aryl Halide Alkene Ratio S/Cat. Yield, % Time, h
PhI n-BuOCOCH=CH2 1000 000 100 (85)a 48
4-MeOC6H4Br n-BuOCOCH=CH2 10 000 100 (88)a 48
4-MeOC6H4Br C6H5CH=CH2 100 000 65a 20
4-CH(O)C6H4Br n-BuOCH=CH2 250 100 (83)a 20
4-CH(O)C6H4Br n-BuOCH=CH2 1000 41a 20

a - isolated yield, conditions: 1 Pd / 1 Tetraphos Fc(P)4, Xylene, K2CO3, 130 °C.


  • Alkynylation of aryl halides (Heck-Sonogashira reaction) under low (10-1 to 10-4 mol%) catalyst loadings in the presence of a Triphos Fc(P)2PiPr EN400-15233 with TONs up to 250000. Copper-free coupling using phenyl- acetylene is also accessible in good yield.

    J.-C. Hierso, V. Ivanov et al., Organic Letters (2004), 6(20), 3473-3476.
    H. Doucet, J.-C. Hierso, Angewandte Chemie International Edition (2007), 46, 834-871.

Aryl Halide Alkyne Ratio S/Cat. Yield, %
PhI phenylacetylene 100000 95
4-Bromoacetophenone phenylacetylene 100000 94
4-Bromobenzonitrile phenylacetylene 10000 89
4-Chlorobenzonitrile phenylacetylene 250 86a
4-Bromoanisole
phenylacetylene 250 93
4-Bromoacetophenone
but-1-yn-4-ol 250 92b
aReaction performed without CuI.
bReaction performed at 100 °C / Conditions: catalyst {Pd(C3H5)Cl}2/Triphos Fc(P)2Pi-Pr 1/2, aryl halide (1 mmol), alkyne (2 mmol), CuI (0.05 mmol), K2CO3 (2 mmol), DMF, 130 °C, 20 h, isolated yields.

 

  • Selective Amination of allylic acetates under low catalyst loadings in the presence of ferrocenyldiphosphine Diphos Fc(PFuMe)2 EN400-15236

    J.-C. Hierso et al. Advanced Synthesis and Catalysis (2005), 347(9), 1198-1202.
    J.-C. Hierso, H. Doucet et al. Tetrahedron (2005), 61, 9759-9766.

Acetate Amine Ratio S/Cat. Conditions Conversion, % Selectivity TOF (h-1)
Allyl acetate aniline 100 Rt, 1h 100 96/4 10000
Allyl acetate piperidine 10000 Rt, 1h 100 - 5000
Allyl acetate morpholine 10000 Rt, 2h 85 100 4250
Allyl acetate diisopropylamine 1000 80 °C 2h 96 100 480
Hex-2-en-1-yl acetate pyrrolidine 1000 50 °C, 20h 100 93/7(lin/br) -
Hex-2-en-1-yl acetate morpholine 1000 50 °C, 20h 98 94/6(lin/br) -
Cinnamyl acetate pyrrolidine 1000 50 °C, 20h 100 94/6(lin/br) 2600
Cinnamyl acetate morpholine 1000 50 °C, 20h 100 93/7(lin/br) 4800
Cinnamyl acetate diethylamine 1000 Rt, 20h 100 94/6(lin/br) 7600
Geranyl acetate morpholine 1000 80 °C, 3h 100 98 33

Catalyst {Pd(C3H5)Cl}2 / Diphos Fc(PFuMe)2 Conditions: S/C = 250-10000, T = 25°C-50 °C, 2 equiv. amine, 1 to 20 h.

 

As reference: see also:
J.-C. Hierso, R. Smaliy et al., Chemical Society Reviews (2007), 36, 1754-1769.
J.-C. Hierso, M. Beauperin, et al., Eur. J. Inorg. Chem. (2007), 3767–3780.



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